EP1237531A1 - Bleaching composition for keratinic fibres, containing a thickening polymer with an ether plastic skeleton - Google Patents

Bleaching composition for keratinic fibres, containing a thickening polymer with an ether plastic skeleton

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Publication number
EP1237531A1
EP1237531A1 EP00981415A EP00981415A EP1237531A1 EP 1237531 A1 EP1237531 A1 EP 1237531A1 EP 00981415 A EP00981415 A EP 00981415A EP 00981415 A EP00981415 A EP 00981415A EP 1237531 A1 EP1237531 A1 EP 1237531A1
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EP
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Prior art keywords
composition according
composition
aminoplast
polymer
radical
Prior art date
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Granted
Application number
EP00981415A
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German (de)
French (fr)
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EP1237531B1 (en
Inventor
Frédéric Legrand
Delphine Allard
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LOreal SA
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LOreal SA
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Classifications

    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/84Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
    • A61K8/88Polyamides
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/84Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00Preparations for care of the hair
    • A61Q5/08Preparations for bleaching the hair

Definitions

  • the present invention relates to a composition for bleaching keratin fibers and in particular human keratin fibers such as the hair, comprising at least one oxidizing agent and at least one thickening polymer with an aminoplast-ether skeleton.
  • bleaching compositions containing one or more oxidizing agents It is known to bleach keratin fibers and in particular human hair, with bleaching compositions containing one or more oxidizing agents.
  • oxidizing agents conventionally used, mention may be made of hydrogen peroxide or of compounds capable of producing hydrogen peroxide by hydrolysis, such as urea peroxide or persalts such as perborates, percarbonates and persulfates, hydrogen peroxide and persulfates being particularly preferred.
  • Said bleaching compositions are mainly in the form of anhydrous products (powders or creams) containing alkaline compounds (amines and alkali silicates), and a peroxygenated reagent such as persulfates,
  • the bleaching compositions can also result from the mixture, at the time of use, of the anhydrous peroxygenated reagent powder with an aqueous composition containing the alkaline compounds and another aqueous composition containing the hydrogen peroxide.
  • the bleaching compositions are also in the form of thickened aqueous compositions of hydrogen peroxide, ready to use.
  • ready-to-use composition is meant, within the meaning of the invention, the composition intended to be applied as it is to keratin fibers, that is to say that it can be stored as it is before use or result from extemporaneous mixture of two or more compositions.
  • keratin fibers that is to say that it can be stored as it is before use or result from extemporaneous mixture of two or more compositions.
  • HLB Hydrophilic Lipophilic Balance
  • a subject of the present invention is thus a ready-to-use composition for bleaching keratin fibers, in particular human keratin fibers, such as the hair, comprising, in a medium suitable for bleaching, at least one oxidizing agent, which is characterized in that it also contains at least one polymer with an aminoplast-ether skeleton.
  • said composition is anhydrous or aqueous.
  • the polymer with an aminoplast-ether backbone can be present in an anhydrous composition in the form of preferably powdery powder or cream and / or in one or more aqueous compositions.
  • the polymer with an aminoplast-ether skeleton is present in at least one aqueous composition which is mixed at the time of use with an anhydrous composition in the form of powder or cream containing at least one oxidizing agent.
  • anhydrous composition in the form of powder or cream containing at least one oxidizing agent.
  • one of these aqueous compositions mixed with the anhydrous composition contains hydrogen peroxide.
  • the invention also relates to a process for bleaching keratin fibers, and in particular human keratin fibers such as the hair, using the ready-to-use bleaching composition as described according to the invention.
  • the invention also relates to bleaching devices or "Kits" for packaging containing such a ready-to-use composition.
  • a device with two compartments comprises a first compartment containing at least one powder or an anhydrous cream or an aqueous composition, and the second compartment an aqueous composition, at least one of the two compartments containing at least one oxidizing agent and the at least one of the two compartments containing at least one polymer with an aminoplast-ether skeleton.
  • Another "kit" with several compartments may consist of a first compartment containing an anhydrous powder or cream and two other compartments each containing an aqueous composition, at least one of the three compartments containing at least one oxidizing agent and at least one of the three compartments containing at least one polymer with an aminoplast-ether backbone.
  • aminoplast-ether is understood within the meaning of the present invention, any product resulting from the condensation of an aldehyde with an amine or an amide.
  • aminoplast-ether is also meant in the sense of the present invention, any structural unit formed of an aminoplast residue and a divalent hydrocarbon residue linked to the aminoplast residue by an ether bond.
  • polymers with an aminoplast-ether skeleton used according to the invention are preferably chosen from those containing at least one unit of structure (I) below:
  • -AMP is an aminoplast residue with alkylene units
  • -R denotes a hydrogen atom, a C-1C4 alkyl radical or an acyl radical
  • -RO- is a divalent alkyleneoxy residue
  • -p denotes a positive integer
  • the group or groups OR being linked to the alkylene units of the AMP residue.
  • the polymers with an aminoplast-ether skeleton are chosen from those containing at least one unit of structure (II) as follows:
  • - RO2 is a hydrophobic group different from RO linked to AMP via a heteroatom and comprising at least two carbon atoms, and, -q is a positive integer.
  • the polymers of the invention have the following formulas (III) and (III) bis:
  • R3 identical or different, represent a terminal group which can denote a hydrogen atom, a group RO-j H, a group RO2H, a group AMP (OR) p or any monofunctional group such as alkyl, cycloalkyl, aryl, aralkyl, alkylaryl , alkyloxyalkyle, aryloxyalkyle, cycloalkoxyalkyle, a being a number greater than 1 and preferably greater than 2.
  • aminoplast residues carrying their OR groups integrated into the polymers of the invention can be chosen without limitation from the following structures (IV) to (XV):
  • R1 denotes C1C4 alkyl
  • y is a number at least equal to 2
  • x denotes 0 or 1.
  • aminoplast residue (s) carrying their OR groups are chosen from those of structure (XVI) below:
  • R, p, and x have the same meanings as before.
  • the divalent alkyleneoxy residues are preferably those corresponding to the diols of general formula (XVII) below: HO- (ZO) y- (Z1 (Z2O) w) t- (Z'O) y'-Z3OH (XVII), y and y 'being numbers ranging from 0 to 1000, t and w being numbers ranging from 0 to 10, Z, Z', Z2 and Z3 are C2C4 alkylene radicals and preferably radicals
  • Z1 being a linear or cyclic radical, branched or not, aromatic or not, with or without one or more heteroatoms and having from 1 to 40 carbon atoms, Z4 denoting a hydrogen atom or a C1C4 alkyl radical or a C1C3 acyl radical, it being understood that at least one of the radicals Z4 of the radicals Z, Z ',
  • Z2 and Z3 is different from acyl.
  • the compounds of formula (XVII) are then polyethylene glycols.
  • the polymers with an aminoplast-ether skeleton are preferably used in an amount which can vary from approximately 0.01 to 10% by weight of the total weight of the ready-to-use dye composition. More preferably, this amount varies from about 0.1 to 5% by weight.
  • the oxidizing agents which can be used according to the invention are preferably chosen from hydrogen peroxide and the compounds releasing hydrogen peroxide by hydrolysis, such as urea peroxide and persalts.
  • persulfates and perborates and in particular sodium persulfate or potassium persulfate can be used according to the invention.
  • oxidizing agents mention may be made of chlorites.
  • an enzymatic system generating oxidizing species and in particular hydrogen peroxide mention may be made of oxidoreductases with two electrons associated with their donor in the presence of air, and more particularly the uricase, uric acid and air system.
  • Organic peroxides can also be used.
  • the concentration of hydrogen peroxide in the ready-to-use compositions can vary from 2 to 40 volumes. That of the other oxidizing compounds, in particular the compounds capable of forming hydrogen peroxide by hydrolysis, can vary from 0.1 to 25% by weight approximately relative to the total weight of the composition.
  • composition according to the invention may also contain, in addition to the oxidizing agents defined above, direct dyes.
  • direct dyes can in particular then be chosen from nitro, azo or anthraquinone dyes, whether they are neutral, acidic or cationic.
  • compositions according to the invention may also contain, at least one cationic or amphoteric substantive polymer.
  • cationic polymer designates any polymer containing cationic groups and / or groups which can be ionized into cationic groups.
  • the cationic polymers which can be used in accordance with the present invention can be chosen from all those already known per se as improving the cosmetic properties of the hair, namely in particular those described in patent application EP-A-337 354 and in French patents FR- 2,270,846, 2,383,660, 2,598,611, 2,470,596 and 2,519,863.
  • the preferred cationic polymers are chosen from those which contain units comprising primary, secondary, tertiary and / or quaternary amine groups which can either be part of the main polymer chain or be carried by a lateral substituent directly connected thereto.
  • the cationic polymers used generally have a number average molecular mass of between 500 and 5.10 6 approximately, and preferably between 10 3 and 3.10 6 approximately.
  • the cationic polymers mention may more particularly be made of polymers of the polyamine, polyaminoamide and quaternary polyammonium type. These are known products. They are described in particular in French patents 2,505,348 or 2,542,997.
  • the said polymers there may be mentioned:
  • R3 identical or different, denote a hydrogen atom or a CH3 radical
  • A identical or different, represent an alkyl group, linear or branched, from 1 to 6 carbon atoms, preferably 2 or 3 carbon atoms or a hydroxyalkyl group from 1 to 4 carbon atoms;
  • Rl and R2, identical or different represent hydrogen or an alkyl group having from 1 to 6 carbon atoms and preferably methyl or ethyl;
  • X denotes an anion derived from a mineral or organic acid such as a methosulfate anion or a halide such as chloride or bromide.
  • the polymers of family (1) can also contain one or more units deriving from comonomers which can be chosen from the family of acrylamides, methacrylamides, diacetones, acrylamides, acrylamides and methacrylamides substituted on nitrogen by lower alkyls (C1 -C4) , acrylic or methacrylic acids or their esters, vinyllactams such as vinylpyrrolidone or vinylcaprolactam, vinyl esters.
  • comonomers which can be chosen from the family of acrylamides, methacrylamides, diacetones, acrylamides, acrylamides and methacrylamides substituted on nitrogen by lower alkyls (C1 -C4) , acrylic or methacrylic acids or their esters, vinyllactams such as vinylpyrrolidone or vinylcaprolactam, vinyl esters.
  • Cationic cellulose derivatives such as cellulose copolymers or cellulose derivatives grafted with a water-soluble quaternary ammonium monomer, and described in particular in US Pat. No. 4,131,576, such as hydroxyalkyl celluloses, such as hydroxymethyl- , hydroxyethyl- or hydroxypropyl celluloses grafted in particular with a salt of methacryloylethyl trimethylammonium, of methacrylmidopropyl trimethylammonium, of dimethyl-diallylammonium.
  • cationic polysaccharides described more particularly in US patents 3,589,578 and 4,031,307 such as guar gums containing cationic trialkylammonium groups.
  • Guar gums modified with a salt (eg chloride) of 2,3-epoxypropyl trimethylammonium are used, for example.
  • Such products are marketed in particular under the trade names of JAGUAR C13 S, JAGUAR C 15, JAGUAR C 17 or JAGUAR C162 by the company MEYHALL.
  • Polymers consisting of piperazinyl units and divalent alkylene or hydroxyalkylene radicals with straight or branched chains, optionally interrupted by oxygen, sulfur, nitrogen atoms or by aromatic or heterocyclic rings, as well as the products of oxidation and / or quaternization of these polymers.
  • Such polymers are described in particular in French patents 2,162,025 and 2,280,361.
  • Water-soluble polyaminoamides prepared in particular by polycondensation of an acidic compound with a polyamine; these polyaminoamides can be crosslinked with an epihalohydrin, a diepoxide, a dianhydride, an unsaturated dianhydride, a bis-unsaturated derivative, a bis-halohydne, a bis-azetidinium, a bis-haloacyldiamine, a bis-halide of alkyl or also with an oligomer resulting from the reaction of a bifunctional compound reactive with a bis-halohydrin, a bis-azetidinium, a bis-haloacyldiamine, an alkyl bis-halide, an epilhalohydrin, a diepoxide or a bis-unsaturated derivative; the crosslinking agent being used in proportions ranging from 0.025 to 0.35 mole per amino group of the polyaminoamide; these polyaminoamides can be
  • Polyaminoamide derivatives resulting from the condensation of polyalkylene polyamines with polycarboxylic acids followed by alkylation by bifunctional agents Mention may be made, for example, of the adipic acid-diacoylaminohydroxyalkoyldialoylene triamine polymers in which the alkyl radical contains from 1 to 4 carbon atoms and preferably denotes methyl, ethyl, propyl. Such polymers are described in particular in French patent 1,583,363. Among these derivatives, there may be mentioned more particularly the adipic acid / dimethylaminohydroxypropyl / diethylene triamine polymers sold under the name "Cartaretine F, F4 or F8" by the company Sandoz.
  • the molar ratio between the polyalkylene polylamine and the dicarboxylic acid being between 0.8: 1 and 1.4: 1; the resulting polyaminoamide being reacted with epichlorohydrin in a molar ratio of epichlorohydrin relative to the secondary amino group of the polyaminoamide of between 0.5: 1 and 1.8: 1.
  • Such polymers are described in particular in the patents American 3,227,615 and 2,961,347.
  • Polymers of this type are in particular sold under the name "Hercosett 57” by the company Hercules Inc. or else under the name of "PD 170” or “Delsette 101” by the company Hercules in the case of the adipic acid copolymer / epoxypropyl / diethylenetriamine.
  • R 9 denotes a hydrogen atom or a methyl radical
  • R and R 8 independently of one another, denote an alkyl group having from 1 to 22 carbon atoms, a hydroxyalkyl group in which the alkyl group preferably has 1 to 5 carbon atoms, a lower amidoalkyl group (C1-C4), or R7 and Rg may denote jointly with the nitrogen atom to which they are attached , heterocyclic groups, such as piperidinyl or morpholinyl;
  • R 7 and Rg independently of one another, preferably denote an alkyl group having from 1 to 4 carbon atoms;
  • Y " is an anion such as bromide, chloride, acetate, borate, citrate, tartrate, bisulfate, bisulfite, sulfate, phosphate.
  • R12 e * R13 represent a linear or branched C ⁇ -CQ alkyl radical substituted by a nitrile, ester, acyl, amide or -CO-O- R14-D or -CO-NH- R14-D group where R14 is an alkylene and D a quaternary ammonium group;
  • A1 and B1 represent polymethylenic groups containing from 2 to 20 carbon atoms which may be linear or branched, saturated or unsaturated, and which may contain, linked to or intercalated in the main chain, one or more aromatic rings, or one or more atoms of oxygen, sulfur or sulfoxide, sulfone, disulfide, amino, alkylamino, hydroxyl, quaternary ammonium, ureido, amide or ester groups, and
  • 2 can form with the two nitrogen atoms to which they
  • x and y denote an integer from 1 to 4, representing a defined and unique degree of polymerization or any number from 1 to 4 representing an average degree of polymerization; b) a bis-secondary diamine residue such as a piperazine derivative; c) a bis-primary diamine residue of formula: -NH-Y-NH-, where Y denotes a linear or branched hydrocarbon radical, or else the bivalent radical
  • X ⁇ is an anion such as chloride or bromide.
  • These polymers have a number average molecular weight generally between 1000 and 100,000.
  • R 11 R 12 e * R 13, identical or different, denote an alkyl or hydroxyalkyl radical having from 1 to 4 carbon atoms approximately, n and p are whole numbers varying from 2 to 20 approximately and, X - is an anion derived from a mineral or organic acid.
  • cationic polymers comprising units of formula (IX) are described in particular in patent application EP-A-122 324 and can be prepared according to the methods described in US patents No. 4,157,388, 4,390,689, 4,702,906 , 4,719,282.
  • the polymer with units of formula (IX) in which p is equal to 3 is preferred, D denotes the value zero, X denotes a chlorine atom, the molecular mass measured by NMR of Carbon 13,
  • Quaternary polymers of vinylpyrrolidone and of vinylimidazole such as for example the products marketed under the names Luviquat FC 905, FC 550 and FC 370 by the company B.A.S.F.
  • Crosslinked polymers of methacryloyioxyalkyl (C ⁇ -C4) trialkyl (C ⁇ - C4) ammonium salts such as the polymers obtained by homopolymerization of dimethylaminoethylmethacrylate quaternized with methyl chloride, or by copolymerization of acrylamide with dimethylaminoethylmethacrylate quaternized with methyl chloride, homo or copolymerization being followed by crosslinking with an olefinically unsaturated compound, in particular methylene bis acrylamide .
  • This dispersion is marketed under the name of
  • SALCARE® SC 92 by the company ALLIED COLLOIDS. It is also possible to use a crosslinked homopolymer of methacryloyloxyethyl trimethylammonium chloride containing approximately 50% by weight of the homopolymer in mineral oil or in a liquid ester. These dispersions are marketed under the names of "SALCARE® SC 95” and “SALCARE® SC 96" by the company ALLIED COLLOIDS.
  • cationic polymers which can be used in the context of the invention are polyalkyleneimines, in particular polyethyleneimines, polymers containing vinylpyridine or vinylpyridinium units, polyamine and epichlorohydrin condensates, quaternary polyuretylenes and chitin derivatives.
  • cationic polymers capable of being used in the context of the present invention, it is preferred to use the polymers of families (1), (9), (10) (11) and (14) and even more preferably the polymers of formulas (W) and (U) below:
  • CH 3 C 2 H 5 and in particular those whose molecular weight, determined by gel permeation chromatography, is approximately 1200.
  • the concentration of cationic polymer in the compositions according to the present invention can vary from 0.01 to 10% by weight relative to the total weight of the composition, preferably from 0.05 to 5% and even more preferably from 0.1 to 3%.
  • amphoteric polymers which can be used in accordance with the present invention can be chosen from polymers comprising K and M units distributed statistically in the polymer chain, where K denotes a unit derived from a monomer comprising at least one basic nitrogen atom and M denotes a unit deriving from an acid monomer comprising one or more carboxylic or sulphonic groups, or else K and M may denote groups deriving from zwitterionic monomers of carboxybetaines or of sulphobetaines; K and M can also denote a cationic polymer chain comprising primary, secondary, tertiary or quaternary amine groups, in which at least one of the amine groups carries a carboxylic or sulphonic group linked via a hydrocarbon radical, or although K and M form part of a chain of a polymer with an ⁇ , ⁇ -dicarboxylic ethylene unit, one of the carboxyl groups of which has been reacted with a polyamine comprising one or more primary or
  • amphoteric film-forming polymers corresponding to the definition given above which are more particularly preferred are chosen from the following polymers:
  • the vinyl compound can also be a dialkyldiallylammonium salt such as dimethyldiallylammonium chloride.
  • a dialkyldiallylammonium salt such as dimethyldiallylammonium chloride.
  • Polymers comprising units derived from: a) at least one monomer chosen from acrylamides or methacrylamides substituted on nitrogen by an alkyl radical, b) from at least one acidic comonomer containing one or more carboxylic groups reactants, and c) at least one basic comonomer such as esters with primary, secondary, tertiary and quaternary amine substituents of acrylic and methacrylic acids and the quaternization product of dimethylaminoethyl methacrylate with dimethyl or diethyl sulfate.
  • the N-substituted acrylamides or methacrylamides more particularly preferred according to the invention are the groups in which the alkyl radicals contain from 2 to 12 carbon atoms and more particularly N-ethylacrylamide, N-tertiobutyl-acrylamide, N-tertiooctyl-acrylamide , N-octylacrylamide, N-decylacrylamide, N-dodecylacrylamide and the corresponding methacrylamides.
  • the acid comonomers are chosen more particularly from acrylic, methacrylic, crotonic, itaconic, maleic, fumaric acids as well as alkyl monoesters having 1 to 4 carbon atoms of maleic or fumaric acids or anhydrides.
  • the preferred basic comonomers are aminoethyl, butyl aminoethyl, N, N'-dimethylaminoethyl, N-tert-butylaminoethyl methacrylates.
  • Copolymers are particularly used whose name CTFA (4th Ed., 1991) is Octylacrylamide / acrylates / butylaminoethylmethacrylate copolymer such as the products sold under the name AMPHOMER or LOVOCRYL 47 by the company NATIONAL STARCH.
  • Rj g represents a divalent radical derived from a saturated dicarboxylic acid, from a mono or dicarboxylic acid with ethylene double bond, from an ester of a lower alkanol having 1 to 6 carbon atoms of these acids or d 'a radical derived from the addition of any one of said acids with a primary bis or secondary bis amino
  • Z denotes a radical of a bis-primary, mono or bis-secondary polyalkylene polyamine and preferably represents: a ) in the proportions of 60 to 100 mol%, the radical
  • the saturated carboxylic acids are preferably chosen from acids having 6 to 10 carbon atoms such as adipic, trimethyl-2,2,4-adipic acid and trimethyl-2,4,4-adipic, terephthalic acid, ethylenic double bond such as for example acrylic, methacrylic, itaconic acids.
  • the alkane sultones used in the alkylation are preferably propane or butane sultone, the salts of the alkylating agents are preferably the sodium or potassium salts.
  • R20 denotes a polymerizable unsaturated group such as an acrylate, methacrylate, acrylamide or methacrylamide group
  • y and z represent an integer from 1 to 3
  • R21 and R22 represent a hydrogen, methyl, ethyl or propyl atom
  • R23 and R24 represent one. hydrogen atom or an alkyl radical such that the sum of the carbon atoms in R23 and R24 does not exceed 10.
  • the polymers comprising such units may also contain units derived from non-zwitterionic monomers such as acrylate or dimethyl or diethylaminoethyl methacrylate or alkyl acrylates or methacrylates, acrylamides or methacrylamides or vinyl acetate.
  • the copolymer of methyl methacrylate / methyl dimethyl-carboxymethylammonio-ethyl methacrylate such as the product sold under the name DIAFORMER Z301 by the company SANDOZ.
  • R 25 represents a radical of formula:
  • ⁇ / and X denotes the symbol E or E ', E or E', which are identical or different, denote a bivalent radical which is an alkylene radical with a straight or branched chain containing up to 7 carbon atoms in the unsubstituted main chain or substituted by hydroxyl groups and which may also contain oxygen, nitrogen, sulfur atoms, 1 to 3 aromatic and / or heterocyclic rings; the oxygen, nitrogen and sulfur atoms being present in the form of ether, thioether, sulfoxide, sulfone, sulfonium, alkylamine, alkenylamine groups, hydroxyl groups, benzylamine, amine oxide, quaternary ammonium, amide, imide, alcohol, ester and / or urethane;
  • E denotes the symbol E or E 'and at least once E';
  • E having the meaning indicated above and E 'is a bivalent radical which is a straight or branched chain alkylene radical having up to 7 carbon atoms in the main chain, substituted or not by one or more hydroxyl radicals and comprising a or more nitrogen atoms, the nitrogen atom being substituted by an alkyl chain optionally interrupted by an oxygen atom and necessarily having one or more carboxyl functions or one or more hydroxyl functions and betainized by reaction with chloracetic acid or sodium chloracetate.
  • amphoteric polymers which are particularly preferred according to the invention are those of the family (1).
  • the amphoteric polymer (s) can represent from 0.01% to 10% by weight, preferably from 0.05% to 5% by weight, and even more preferably from 0.1% to 3% by weight , of the total weight of the composition.
  • compositions of the invention preferably comprise one or more surfactants.
  • the surfactant (s) can be chosen either, alone or as a mixture, from anionic, amphoteric, nonionic, zwitterionic and cationic surfactants.
  • surfactants which are suitable for carrying out the present invention are in particular the following:
  • anionic surfactants which can be used, alone or as mixtures, in the context of the present invention, there may be mentioned in particular (non-limiting list) the salts (in particular alkaline salts, in particular sodium salts, ammonium salts, amine salts, amino alcohol salts or magnesium salts) of the following compounds: alkylsulphates, alkylethersulphates, alkylamidoethersulphates, alkylarylpolyethersulphates, monoglycerides sulphates; alkylsulfonates, alkylphosphates, alkylamidesulfonates, alkylarylsulfonates, ⁇ -olefin-sulfonates, paraffin-sulfonates; alkyl (C ⁇ -C 2 ) sulfosuccinates, alkyl (C 6 -C 2 ) ethersulfosuccinates, alkyl (C 6 -C 24 ) amidesulfosuccinate
  • alkyl esters (C6-C 2 ) carboxylic polyglycosides such as the alkylglucoside citrates, the alkylpolyglycoside tartrate and the alkylpolyglycoside sulfosuccinates.
  • anionic surfactants which can still be used, mention may also be made of the salts of fatty acids such as the salts of oleic, ricinoleic and palmitic acids, stearic acid from coconut oil or hydrogenated coconut oil; acyl lactylates whose acyl radical contains 8 to 20 carbon atoms.
  • alkyl D galactoside uronic acids and their salts it is also possible to use the alkyl D galactoside uronic acids and their salts, the polyoxyalkylenated (C 6 -C 24 ) alkyl ether carboxylic acids, the polyoxyalkylenated (C 6 - C 2 ) aryl ether carboxylic acids, the alkyl (C 6 -C 24 ) polyoxyalkylenated carboxylic amido ether and their salts, in particular those comprising from 2 to 50 alkylene oxide groups, in particular ethylene, and their mixtures.
  • Non-ionic surfactants are also well known compounds per se (see in particular in this regard "Handbook of Surfactants” by MR PORTER, Blackie & Son editions (Glasgow and London), 1991, pp 116-178) and their nature is not, in the context of the present invention, critical. Thus, they can in particular be chosen from (nonlimiting list) alcohols, alpha-diols, polyethoxylated, polypropoxylated alkylphenols, having a fatty chain comprising for example 8 to 18 carbon atoms, the number of ethylene oxide groups or propylene oxide which can range in particular from 2 to 50.
  • the alkylpolyglycosides constitute nonionic surfactants which are particularly well suited to the present invention.
  • Amphoteric or zwitterionic surfactant (s) may in particular be (non-limiting list) derivatives of aliphatic secondary or tertiary amines, in which the aliphatic radical is a chain linear or branched having 8 to 18 carbon atoms and containing at least one water-soluble anionic group (for example carboxylate, sulfonate, sulfate, phosphate or phosphonate); mention may also be made of (C8-C20) alkyl betaines, sulfobetaines, (C8-C20) alkyl amidoalkyl (C -CQ) betaines or (C ⁇ -C20) amidoalkyl (C1-C5) sulfobetaines alkyl.
  • aliphatic secondary or tertiary amines in which the aliphatic radical is a chain linear or branched having 8 to 18 carbon atoms and containing at least one water-soluble anionic group (for example carboxy
  • B represents -CH2CH2OX '
  • C represents - (CH2) Z -Y'
  • z 1 or 2
  • Y' denotes -COOH or the radical -CH 2 - CHOH - SO3H
  • R34 ′ denotes an alkyl radical of an acid R37 -COOH present in coconut oil or in hydrolyzed linseed oil, an alkyl radical, in particular C7, Cg, Cj 1 or C-13, an alkyl radical in C-17 and its iso form, an unsaturated C-J7 radical.
  • These compounds are classified in the CTFA dictionary, 5th edition, 1993, under the names Disodium Cocoamphodiacetate, Disodium Lauroampho- diacetate, Disodium Caprylamphodiacetate, Disodium Capryloamphodiacetate, Disodium Cocoamphodipropionate, Disodium Lauroamphodipropionate, Disodium Capryl. Lauroampho- dipropionic acid, Cocoamphodipropionic acid.
  • cocoamphodiacetate sold under the trade name MIRANOL® C2M concentrated by the company RHODIA CHIMIE.
  • cationic surfactants that may be mentioned in particular (nonlimiting list): the salts of primary, secondary or tertiary fatty amines, optionally polyoxyalkylenated; quaternary ammonium salts such as chlorides or bromides of tetraalkylammonium, alkylamidoalkyltrialkylammonium, trialkylbenzylammonium, trialkylhydroxyalkylammonium or alkylpyridinium; imidazoline derivatives; or amine oxides of a cationic nature.
  • the amounts of surfactants present in the ready-to-use composition according to the invention can vary from 0.01 to 40% and preferably from 0.1 to 30% of the total weight of the composition.
  • compositions according to the invention may also contain other rheology adjusting agents such as cellulosic thickeners
  • Pemulen TR1 or TR2 by the company Goodrich
  • Salcare SC90 by the company ALLIED COLLOIDS
  • ACULYN 22, 28, 33, 44, or 46 by the company ROHM & HAAS and ELFACOS T210 and T212 by the
  • These additional thickeners can represent from 0.05 to 10% by weight of the total weight of the composition.
  • compositions according to the invention also advantageously contain an alkaline agent.
  • basifying agents there may be mentioned, by way of example, ammonia, ammonium chloride, alkali or alkaline earth carbonates, alkali or alkaline earth silicates, alkaline or alkaline earth phosphates, alkanolamines such as mono-, di- and triethanolamines as well as their derivatives, sodium or potassium hydroxides and the compounds of formula (XIX) below:
  • R is a propylene residue optionally substituted by a hydroxyl group or a C- ⁇ -C alkyl radical;
  • R 38 , R 39 , R 4 o and R 4 ⁇ identical or different,.
  • compositions of the invention can also contain sequestering agents such as for example ethylenediamine tetraacetic acid (EDTA).
  • sequestering agents such as for example ethylenediamine tetraacetic acid (EDTA).
  • compositions containing the oxidizing agent and the polymer with an aminoplast-ether skeleton are in anhydrous form (powder or cream), they contain the main agents and additives mentioned above in the form of essentially anhydrous solids or liquids. They can also contain mineral or organic fillers such as silica or clays. They can also contain binders such as vinylpyrrolidone, oils or waxes, polyalkylene glycols or derivatives of polyalkylene glycols. They may also contain lubricants such as polyol stearates or alkali or alkaline earth metal sterates, as well as coloring or matifying agents such as titanium oxides.
  • the medium containing the oxidizing agent may optionally contain cosmetically acceptable organic solvents, including more particularly, alcohols such as ethyl alcohol, isopropyl alcohol, benzyl alcohol, and phenylethyl alcohol, or glycols or glycol ethers such as, for example, monomethyl, monoethyl and monobutyl ethers of ethyleneglycol, propyleneglycol or its ethers such as, for example, propylene glycol monomethyl ether, butylene glycol, dipropylene glycol as well as the diethylene glycol alkyl ethers such as, for example, the monoethyl ether or the monobutyl ether of diethylene glycol, in concentrations of between approximately 0.5 and 20% and, preferably, between approximately 2 and 10% by weight relative to the total weight of the composition.
  • alcohols such as ethyl alcohol, isopropyl alcohol, benzyl alcohol, and phenylethyl alcohol
  • the bleaching composition according to the invention also contains an effective amount of other agents, which have previously been known in bleaching, such as various usual adjuvants such as volatile or non-volatile, cyclic or linear or branched, organomodified silicones (in particular by amino groups ) or not organomodified, preservatives, ceramides, waxes or oils, vegetable, mineral or synthetic, acids and in particular HA A etc.
  • various usual adjuvants such as volatile or non-volatile, cyclic or linear or branched, organomodified silicones (in particular by amino groups ) or not organomodified, preservatives, ceramides, waxes or oils, vegetable, mineral or synthetic, acids and in particular HA A etc.
  • the pH of the ready-to-use composition is generally between the values 4 and 12. It is preferably between 7 and 11, 5 and even more preferably between 8 and 11.
  • the bleaching process according to the invention consists in applying the ready-to-use oxidizing composition to the dry or wet keratin fibers, and to leaving it to act for a pause time varying, preferably, from 1 to 60 minutes approximately, and more preferably 10 to 45 minutes approximately, to rinse the fibers, then optionally to wash them in shampoo, then to rinse them again, and to dry them.
  • the following bleaching composition was prepared (expressed in grams):
  • a ready-to-use bleaching cream was then obtained which, applied and left for 45 minutes under a helmet, made it possible to obtain a powerful and uniform bleaching of dark natural hair.

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Abstract

The present invention relates to a ready to use composition, a process and a kit for bleaching keratin fibers, and in particular human keratin fibers such as the hair, comprising at least one oxidizing agent and at least one thickening polymer with an aminoplast-ether skeleton. This novel composition, process and kit can be used to bleach hair without running or falls in viscosity over time.

Description

COMPOSITION DE DECOLORATION POUR FIBRES KERATINIQUES DECOLORATION COMPOSITION FOR KERATINIC FIBERS
COMPRENANT UN POLYMERE EPAISSISSANTCOMPRISING A THICKENING POLYMER
A SQUELETTE AMINOPLASTE-ETHER.WITH AMINOPLASTE-ETHER SKELETON.
La présente invention concerne une composition pour la décoloration des fibres kératiniques et en particulier des fibres kératiniques humaines telles que les cheveux, comprenant au moins un agent oxydant et au moins un polymère épaississant à squelette aminoplaste-éther.The present invention relates to a composition for bleaching keratin fibers and in particular human keratin fibers such as the hair, comprising at least one oxidizing agent and at least one thickening polymer with an aminoplast-ether skeleton.
II est connu de décolorer les fibres kératiniques et en particulier les cheveux humains, avec des compositions de décoloration contenant un ou plusieurs agents oxydants. Parmi les agents oxydants classiquement utilisés, on peut citer le peroxyde d'hydrogène ou des composés susceptibles de produire le peroxyde d'hydrogène par hydrolyse, tels que le peroxyde d'urée ou les persels comme les perborates, les percarbonates et les persulfates, le peroxyde d'hydrogène et les persulfates étant particulièrement préférés.It is known to bleach keratin fibers and in particular human hair, with bleaching compositions containing one or more oxidizing agents. Among the oxidizing agents conventionally used, mention may be made of hydrogen peroxide or of compounds capable of producing hydrogen peroxide by hydrolysis, such as urea peroxide or persalts such as perborates, percarbonates and persulfates, hydrogen peroxide and persulfates being particularly preferred.
Lesdites compositions de décoloration se présentent principalement sous forme de produits anhydres ( poudres ou crèmes ) contenant des composés alcalins (aminés et silicates alcalins), et un réactif peroxygéné tels que les persulfates,Said bleaching compositions are mainly in the form of anhydrous products (powders or creams) containing alkaline compounds (amines and alkali silicates), and a peroxygenated reagent such as persulfates,
- perborates ou percarbonates, d'ammonium ou de métaux alcalins, que l'on dilue au moment de l'emploi avec une composition aqueuse de peroxyde d'hydrogène.- Perborates or percarbonates, of ammonium or alkali metals, which are diluted at the time of use with an aqueous composition of hydrogen peroxide.
Les compositions de décoloration peuvent aussi résulter du mélange, au moment de l'emploi, de la poudre anhydre de réactif peroxygéné avec une composition aqueuse contenant les composés alcalins et une autre composition aqueuse contenant le peroxyde d'hydrogène.The bleaching compositions can also result from the mixture, at the time of use, of the anhydrous peroxygenated reagent powder with an aqueous composition containing the alkaline compounds and another aqueous composition containing the hydrogen peroxide.
Les compositions de décoloration se présentent également sous forme de compositions aqueuses épaissies de peroxyde d'hydrogène, prêtes à l'emploi.The bleaching compositions are also in the form of thickened aqueous compositions of hydrogen peroxide, ready to use.
Par "composition prête à l'emploi" on entend, au sens de l'invention, la composition destinée à être appliquée telle quelle sur les fibres kératiniques, c'est à dire qu'elle peut être stockée telle quelle avant utilisation ou résulter du mélange extemporané de deux ou plusieurs compositions. Pour localiser le produit de décoloration à l'application sur les cheveux afin qu'il ne coule pas sur le visage ou en dehors des zones que Ton se propose de décolorer, on a jusqu'ici eu recours à l'emploi d'épaississants traditionnels tels que l'acide polyacrylique réticulé, les hydroxyéthylcelluloses, certains polyuréthanes, les cires, et en outre, dans le cas des compositions aqueuses de décoloration, à des mélanges d'agents tensio-actifs non-ioniques de HLB (Hydrophilic Lipophilic Balance), qui, convenablement choisis, engendrent l'effet gélifiant quand on les dilue au moyen d'eau et/ou d'agents tensio-actifs.By “ready-to-use composition” is meant, within the meaning of the invention, the composition intended to be applied as it is to keratin fibers, that is to say that it can be stored as it is before use or result from extemporaneous mixture of two or more compositions. To localize the bleaching product when applied to the hair so that it does not run on the face or outside the areas which it is proposed to bleach, use of traditional thickeners has hitherto been used. such as crosslinked polyacrylic acid, hydroxyethylcelluloses, certain polyurethanes, waxes, and in addition, in the case of aqueous bleaching compositions, to mixtures of nonionic surfactants of HLB (Hydrophilic Lipophilic Balance), which, suitably chosen, generate the gelling effect when diluted with water and / or surfactants.
Cependant, la demanderesse a constaté que les systèmes épaississants mentionnés ci-dessus ne permettaient pas d'obtenir des décolorations suffisamment puissantes et homogènes et laissaient les cheveux rèches. Par ailleurs, elle a également constaté que les compositions de décoloration prêtes à l'emploi contenant le ou les agents oxydants, et en outre les systèmes épaississants de l'art antérieur ne permettaient pas une application suffisamment précise sans coulures ni chutes de viscosité dans le temps.However, the Applicant has found that the thickening systems mentioned above did not make it possible to obtain sufficiently powerful and homogeneous bleaches and left the hair coarse. Furthermore, it also found that the ready-to-use bleaching compositions containing the oxidizing agent (s), and in addition the thickening systems of the prior art did not allow a sufficiently precise application without drips or drops in viscosity in the time.
Or, après d'importantes recherches menées sur la question, la Demanderesse vient maintenant de découvrir qu'il est possible d'obtenir des compositions de décoloration prêtes à l'emploi qui ne coulent pas et restent donc bien localisées au point d'application, et qui permettent aussi d'obtenir des décolorations puissantes et homogènes tout en laissant les cheveux moins rèches si on introduit dans la composition une quantité efficace d'un polymère à squelette aminoplaste-éther.Now, after significant research carried out on the question, the Applicant has now discovered that it is possible to obtain ready-to-use bleaching compositions which do not flow and therefore remain well located at the point of application, and which also make it possible to obtain powerful and homogeneous bleaches while leaving the hair less coarse if an effective amount of a polymer with an aminoplast-ether skeleton is introduced into the composition.
Ces découvertes sont à la base de la présente invention.These discoveries are the basis of the present invention.
La présente invention a ainsi pour objet une composition prête à l'emploi pour la décoloration des fibres kératiniques, en particulier des fibres kératiniques humaines, telles que les cheveux, comprenant, dans un milieu approprié pour la décoloration, au moins un agent oxydant, qui est caractérisée par le fait qu'elle contient en outre au moins un polymère à squelette aminoplaste-éther. Selon l'invention, ladite composition est anhydre ou aqueuse. Lorsque la composition prête à l'emploi selon l'invention résulte du mélange extemporané de plusieurs compositions, le polymère à squelette aminoplaste- éther peut être présent dans une ou plusieurs ou dans la totalité des compositions mélangées.A subject of the present invention is thus a ready-to-use composition for bleaching keratin fibers, in particular human keratin fibers, such as the hair, comprising, in a medium suitable for bleaching, at least one oxidizing agent, which is characterized in that it also contains at least one polymer with an aminoplast-ether skeleton. According to the invention, said composition is anhydrous or aqueous. When the ready-to-use composition according to the invention results from the extemporaneous mixture of several compositions, the polymer with an aminoplast-ether skeleton may be present in one or more or in all of the mixed compositions.
De la sorte, le polymère à squelette aminoplaste-éther peut être présent dans une composition anhydre sous forme de poudre de préférence pulvérulente ou de crème et/ou dans une ou plusieurs compositions aqueuses.In this way, the polymer with an aminoplast-ether backbone can be present in an anhydrous composition in the form of preferably powdery powder or cream and / or in one or more aqueous compositions.
De préférence selon l'invention, le polymère à squelette aminoplaste-éther est présent dans au moins une composition aqueuse que l'on mélange au moment de l'emploi avec une composition anhydre sous forme de poudre ou de crème contenant au moins un agent oxydant. Plus préférentiellement encore, l'une de ces compositions aqueuses mélangée à la composition anhydre renferme du peroxyde d'hydrogène.Preferably according to the invention, the polymer with an aminoplast-ether skeleton is present in at least one aqueous composition which is mixed at the time of use with an anhydrous composition in the form of powder or cream containing at least one oxidizing agent. . Even more preferably, one of these aqueous compositions mixed with the anhydrous composition contains hydrogen peroxide.
L'invention vise également un procédé de décoloration des fibres kératiniques, et en particulier des fibres kératiniques humaines telles que les cheveux utilisant la composition de décoloration prête à l'emploi telle que décrite selon l'invention.The invention also relates to a process for bleaching keratin fibers, and in particular human keratin fibers such as the hair, using the ready-to-use bleaching composition as described according to the invention.
L'invention vise aussi des dispositifs de décoloration ou "Kits" d'emballage contenant une telle composition prête à l'emploi.The invention also relates to bleaching devices or "Kits" for packaging containing such a ready-to-use composition.
Ainsi, un dispositif à deux compartiments comprend un premier compartiment contenant au moins une poudre ou une crème anhydre ou une composition aqueuse, et le deuxième compartiment une composition aqueuse, l'un au moins des deux compartiments contenant au moins un agent oxydant et l'un au moins des deux compartiments contenant au moins un polymère à squelette aminoplaste-éther.Thus, a device with two compartments comprises a first compartment containing at least one powder or an anhydrous cream or an aqueous composition, and the second compartment an aqueous composition, at least one of the two compartments containing at least one oxidizing agent and the at least one of the two compartments containing at least one polymer with an aminoplast-ether skeleton.
Un autre « kit » à plusieurs compartiments peut être constitué d'un premier compartiment contenant une poudre ou une crème anhydre et de deux autres compartiments contenant chacun une composition aqueuse, l'un au moins des trois compartiments contenant au moins un agent oxydant et l'un au moins des trois compartiments contenant au moins un polymère à squelette aminoplaste- éther.Another "kit" with several compartments may consist of a first compartment containing an anhydrous powder or cream and two other compartments each containing an aqueous composition, at least one of the three compartments containing at least one oxidizing agent and at least one of the three compartments containing at least one polymer with an aminoplast-ether backbone.
Mais d'autres caractéristiques, aspects, objets et avantages de l'invention apparaîtront encore plus clairement à la lecture de la description et des exemples qui suivent.However, other characteristics, aspects, objects and advantages of the invention will appear even more clearly on reading the description and the examples which follow.
Par aminoplaste-éther, on entend au sens de la présente invention, tout produit issu de la condensation d'un aldéhyde avec une aminé ou un amide.By aminoplast-ether is understood within the meaning of the present invention, any product resulting from the condensation of an aldehyde with an amine or an amide.
Par aminoplaste-éther, on entend aussi au sens de la présente invention, toute unité structurale formée d'un résidu aminoplaste et d'un résidu hydrocarboné divalent lié au résidu aminoplaste par une liaison éther.By aminoplast-ether is also meant in the sense of the present invention, any structural unit formed of an aminoplast residue and a divalent hydrocarbon residue linked to the aminoplast residue by an ether bond.
Les polymères à squelette aminoplaste-éther utilisés selon l'invention, sont choisis de préférence parmi ceux contenant au moins un motif de structure (I) suivante :The polymers with an aminoplast-ether skeleton used according to the invention are preferably chosen from those containing at least one unit of structure (I) below:
dans laquelle :in which :
-AMP est un résidu aminoplaste avec unités alkylènes,-AMP is an aminoplast residue with alkylene units,
-R désigne un atome d'hydrogène, un radical alkyl C-1C4 ou un radical acyle-R denotes a hydrogen atom, a C-1C4 alkyl radical or an acyl radical
C1 C4,C1 C4,
-RO- est un résidu alkylèneoxy divalent, -p désigne un nombre entier positif, le ou les groupements OR étant liés aux unités alkylènes du résidu AMP. De préférence, les polymères à squelette aminoplaste-éther sont choisis parmi ceux contenant au moins un motif de structure (II) suivante :-RO- is a divalent alkyleneoxy residue, -p denotes a positive integer, the group or groups OR being linked to the alkylene units of the AMP residue. Preferably, the polymers with an aminoplast-ether skeleton are chosen from those containing at least one unit of structure (II) as follows:
dans laquelle : -AMP, R, RO<| et p ont la même signification que précédemment, where: -AMP, R, RO < | and p have the same meaning as before,
- RO2 est un groupe hydrophobe différent de RO lié à AMP via un hétéroatome et comprenant au moins deux atomes de carbone, et, -q est un nombre entier positif.- RO2 is a hydrophobic group different from RO linked to AMP via a heteroatom and comprising at least two carbon atoms, and, -q is a positive integer.
Plus préférentiellement encore, les polymères de l'invention sont de formules (III) et (lll)bis suivantes :Even more preferably, the polymers of the invention have the following formulas (III) and (III) bis:
R2- (lllbis) R2- (lllbis)
dans lesquelles : AMP, R, RO-1 , RO2, P et q ont la même signification que précédemment, R2 ouin which: AMP, R, RO-1, RO2, P and q have the same meaning as before, R2 or
R3, identiques ou différents représentent un groupe terminal pouvant désigner un atome d'hydrogène, un groupement RO-j H, un groupement RO2H, un groupement AMP(OR)p ou tout groupement monofonctionnel tel que alkyle, cycloalkyle, aryle, aralkyle, alkylaryle, alkyloxyalkyle, aryloxyalkyle, cycloalkoxyalkyle, a étant un nombre plus grand que 1 et de préférence plus grand que 2.R3, identical or different, represent a terminal group which can denote a hydrogen atom, a group RO-j H, a group RO2H, a group AMP (OR) p or any monofunctional group such as alkyl, cycloalkyl, aryl, aralkyl, alkylaryl , alkyloxyalkyle, aryloxyalkyle, cycloalkoxyalkyle, a being a number greater than 1 and preferably greater than 2.
Les résidus aminoplastes porteurs de leurs groupements OR intégrés dans les polymères de l'invention peuvent être choisis de manière non limitative parmi les structures (IV) à (XV) suivantes : The aminoplast residues carrying their OR groups integrated into the polymers of the invention can be chosen without limitation from the following structures (IV) to (XV):
dans lesquelles :in which :
R a la même signification que précédemment,R has the same meaning as before,
R1 désigne alkyle C1C4, y est un nombre au moins égal à 2, x désigne 0 ou 1.R1 denotes C1C4 alkyl, y is a number at least equal to 2, x denotes 0 or 1.
De préférence, le ou les résidus aminoplastes porteurs de leurs groupements OR sont choisis parmi ceux de structure (XVI) suivante :Preferably, the aminoplast residue (s) carrying their OR groups are chosen from those of structure (XVI) below:
dans laquelle R, p , et x ont les mêmes significations que précédemment. in which R, p, and x have the same meanings as before.
Les résidus alkylèneoxy divalents sont de préférence ceux correspondants aux diols de formule générale (XVII) suivante : HO-(ZO)y-(Z1(Z2O)w)t-(Z'O)y'-Z3OH (XVII), y et y' étant des nombres allant de 0 à 1000, t et w étant des nombres allant de 0 à 10, Z, Z', Z2 et Z3 sont des radicaux alkylène en C2C4 et de préférence des radicauxThe divalent alkyleneoxy residues are preferably those corresponding to the diols of general formula (XVII) below: HO- (ZO) y- (Z1 (Z2O) w) t- (Z'O) y'-Z3OH (XVII), y and y 'being numbers ranging from 0 to 1000, t and w being numbers ranging from 0 to 10, Z, Z', Z2 and Z3 are C2C4 alkylene radicals and preferably radicals
-CH2-CH(Z4)- et -CH2-CH(Z4)-CH2-,-CH2-CH (Z4) - and -CH2-CH (Z4) -CH2-,
Z1 étant un radical linéaire ou cyclique, ramifié ou non, aromatique ou non, comportant ou non un ou plusieurs heteroatomes et possédant de 1 à 40 atomes de carbone, Z4 désignant un atome d'hydrogène ou un radical alkyle en C1C4 ou un radical acyle en C1C3 étant entendu qu'au moins un des radicaux Z4 des radicaux Z, Z',Z1 being a linear or cyclic radical, branched or not, aromatic or not, with or without one or more heteroatoms and having from 1 to 40 carbon atoms, Z4 denoting a hydrogen atom or a C1C4 alkyl radical or a C1C3 acyl radical, it being understood that at least one of the radicals Z4 of the radicals Z, Z ',
Z2 et Z3 est différent de acyle.Z2 and Z3 is different from acyl.
De préférence Z4 désigne un atome d'hydrogène ou un radical méthyle. Encore plus préférentiellement t=0 et Z, Z' et Z3 désignent -CH2CH2-, et l'un au moins de y ou y' est différent de 0. Les composés de formule (XVII) sont alors des polyéthylèneglycols.Preferably Z4 denotes a hydrogen atom or a methyl radical. Even more preferably t = 0 and Z, Z 'and Z3 denote -CH2CH2-, and at least one of y or y' is different from 0. The compounds of formula (XVII) are then polyethylene glycols.
Les polymères de formule (I) selon l'invention sont en particulier décrits dans le brevet US 5 914 373 dont le contenu fait partie intégrante de l'invention.The polymers of formula (I) according to the invention are in particular described in US Pat. No. 5,914,373, the content of which forms an integral part of the invention.
Comme polymères à squelette aminoplaste-éther de formule (I), on peut en particulier citer les produits PURE-THIX L [PEG-180/Octoxynol-40/TMMGAs polymers with an aminoplast-ether skeleton of formula (I), mention may in particular be made of the PURE-THIX L products [PEG-180 / Octoxynol-40 / TMMG
Copolymer (Nom INCI)], PURE-THIX M [PEG-180/Laureth-50/TMMG Copolymer (Nom INCI)], et PURE-THIX HH [Polyether-1 (Nom INCI)] vendus par la société SUD-CHEMIE .Copolymer (INCI name)], PURE-THIX M [PEG-180 / Laureth-50 / TMMG Copolymer (INCI name)], and PURE-THIX HH [Polyether-1 (INCI name)] sold by SUD-CHEMIE.
Les polymères à squelette aminoplaste-éther sont utilisés de préférence en une quantité pouvant varier d'environ 0,01 à 10% en poids du poids total de la composition de teinture prête à l'emploi. Plus préférentiellement, cette quantité varie d'environ 0,1 à 5% en poids.The polymers with an aminoplast-ether skeleton are preferably used in an amount which can vary from approximately 0.01 to 10% by weight of the total weight of the ready-to-use dye composition. More preferably, this amount varies from about 0.1 to 5% by weight.
Les agents oxydants utilisables selon l'invention sont choisis de préférence parmi le peroxyde d'hydrogène et les composés libérant du peroxyde d'hydrogène par hydrolyse, tels que le peroxyde d'urée et les persels.The oxidizing agents which can be used according to the invention are preferably chosen from hydrogen peroxide and the compounds releasing hydrogen peroxide by hydrolysis, such as urea peroxide and persalts.
Comme persels on peut utiliser selon l'invention les persulfates et les perborates et en particulier le persulfate de sodium ou le persulfate de potassium. Comme autres agents oxydants on peut citer les chlorites. On peut aussi utiliser un système enzymatique générateur d'espèces oxydantes et en particulier de peroxyde d'hydrogène. Comme exemple de tels systèmes enzymatiques, on peut citer les oxydoréductases à deux électrons associées à leur donneur en présence d'air, et plus particulièrement le système uricase, acide urique et air. On peut aussi utiliser des peroxydes organiques.As persalts, persulfates and perborates and in particular sodium persulfate or potassium persulfate can be used according to the invention. As other oxidizing agents, mention may be made of chlorites. It is also possible to use an enzymatic system generating oxidizing species and in particular hydrogen peroxide. As an example of such enzymatic systems, mention may be made of oxidoreductases with two electrons associated with their donor in the presence of air, and more particularly the uricase, uric acid and air system. Organic peroxides can also be used.
La concentration en peroxyde d'hydrogène des compositions prêtes à l'emploi peut varier de 2 à 40 volumes. Celle des autres composés oxydants dont en particulier les composés susceptibles de former du peroxyde d'hydrogène par hydrolyse peut varier de 0,1 à 25 % en poids environ par rapport au poids total de la composition.The concentration of hydrogen peroxide in the ready-to-use compositions can vary from 2 to 40 volumes. That of the other oxidizing compounds, in particular the compounds capable of forming hydrogen peroxide by hydrolysis, can vary from 0.1 to 25% by weight approximately relative to the total weight of the composition.
La composition selon l'invention peut encore contenir, en plus des agents oxydants définis ci-dessus, des colorants directs. Ces colorants directs peuvent notamment alors être choisis parmi les colorants nitrés, azoïques ou anthraquinoniques, qu'ils soient neutres, acides ou cationiques.The composition according to the invention may also contain, in addition to the oxidizing agents defined above, direct dyes. These direct dyes can in particular then be chosen from nitro, azo or anthraquinone dyes, whether they are neutral, acidic or cationic.
Plus particulièrement, les compositions selon l'invention peuvent en outre contenir, au moins un polymère substantif cationique ou amphotère.More particularly, the compositions according to the invention may also contain, at least one cationic or amphoteric substantive polymer.
Au sens de la présente invention, l'expression "polymère cationique" désigne tout polymère contenant des groupements cationiques et/ou des groupements ionisables en groupements cationiques.Within the meaning of the present invention, the expression “cationic polymer” designates any polymer containing cationic groups and / or groups which can be ionized into cationic groups.
Les polymères cationiques utilisables conformément à la présente invention peuvent être choisis parmi tous ceux déjà connus en soi comme améliorant les propriétés cosmétiques des cheveux, à savoir notamment ceux décrits dans la demande de brevet EP-A-337 354 et dans les brevets français FR-2 270 846, 2 383 660, 2 598 611 , 2 470 596 et 2 519 863.The cationic polymers which can be used in accordance with the present invention can be chosen from all those already known per se as improving the cosmetic properties of the hair, namely in particular those described in patent application EP-A-337 354 and in French patents FR- 2,270,846, 2,383,660, 2,598,611, 2,470,596 and 2,519,863.
Les polymères cationiques préférés sont choisis parmi ceux qui contiennent des motifs comportant des groupements aminé primaire, secondaire, tertiaire et/ou quaternaire pouvant, soit faire partie de la chaîne principale polymère, soit être portés par un substituant latéral directement relié à celle-ci.The preferred cationic polymers are chosen from those which contain units comprising primary, secondary, tertiary and / or quaternary amine groups which can either be part of the main polymer chain or be carried by a lateral substituent directly connected thereto.
Les polymères cationiques utilisés ont généralement une masse moléculaire moyenne en nombre comprise entre 500 et 5.106 environ, et de préférence comprise entre 103 et 3.106 environ. Parmi les polymères cationiques, on peut citer plus particulièrement les polymères du type polyamine, polyaminoamide et polyammonium quaternaire. Ce sont des produits connus. Ils sont notamment décrits dans les brevets français n° 2 505 348 ou 2 542 997. Parmi lesdits polymères, on peut citer :The cationic polymers used generally have a number average molecular mass of between 500 and 5.10 6 approximately, and preferably between 10 3 and 3.10 6 approximately. Among the cationic polymers, mention may more particularly be made of polymers of the polyamine, polyaminoamide and quaternary polyammonium type. These are known products. They are described in particular in French patents 2,505,348 or 2,542,997. Among the said polymers, there may be mentioned:
(1) Les homopolymères ou copolymères dérivés d'esters ou d'amides acryliques ou méthacryliques et comportant au moins un des motifs de formules (I), (II), (III) ou (IV) suivantes:(1) Homopolymers or copolymers derived from acrylic or methacrylic esters or amides and comprising at least one of the units of formulas (I), (II), (III) or (IV):
NNOT
\\
R. R. dans lesquelles:R. R. in which:
R3 , identiques ou différents, désignent un atome d'hydrogène ou un radical CH3;R3, identical or different, denote a hydrogen atom or a CH3 radical;
A, identiques ou différents, représentent un groupe alkyle, linéaire ou ramifié, de 1 à 6 atomes de carbone, de préférence 2 ou 3 atomes de carbone ou un groupe hydroxyalkyle de 1 à 4 atomes de carbone ; R4, R5, R6> identiques ou différents, représentent un groupe alkyle ayant de 1 à 18 atomes de carbone ou un radical benzyle et de préférence un groupe alkyle ayant de 1 à 6 atomes de carbone; R-l et R2 , identiques ou différents, représentent hydrogène ou un groupe alkyle ayant de 1 à 6 atomes de carbone et de préférence méthyle ou éthyle;A, identical or different, represent an alkyl group, linear or branched, from 1 to 6 carbon atoms, preferably 2 or 3 carbon atoms or a hydroxyalkyl group from 1 to 4 carbon atoms; R4, R5, R6 > identical or different, represent an alkyl group having from 1 to 18 carbon atoms or a benzyl radical and preferably an alkyl group having from 1 to 6 carbon atoms; Rl and R2, identical or different, represent hydrogen or an alkyl group having from 1 to 6 carbon atoms and preferably methyl or ethyl;
X désigne un anion dérivé d'un acide minéral ou organique tel qu'un anion méthosulfate ou un halogénure tel que chlorure ou bromure.X denotes an anion derived from a mineral or organic acid such as a methosulfate anion or a halide such as chloride or bromide.
Les polymères de la famille (1) peuvent contenir en outre un ou plusieurs motifs dérivant de comonomères pouvant être choisis dans la famille des acrylamides, méthacrylamides, diacétones acrylamides, acrylamides et méthacrylamides substitués sur l'azote par des alkyles inférieurs (C1 -C4), des acides acryliques ou méthacryliques ou leurs esters, des vinyllactames tels que la vinylpyrrolidone ou le vinylcaprolactame, des esters vinyliques. Ainsi, parmi ces polymères de la famille (1), on peut citer :The polymers of family (1) can also contain one or more units deriving from comonomers which can be chosen from the family of acrylamides, methacrylamides, diacetones, acrylamides, acrylamides and methacrylamides substituted on nitrogen by lower alkyls (C1 -C4) , acrylic or methacrylic acids or their esters, vinyllactams such as vinylpyrrolidone or vinylcaprolactam, vinyl esters. Thus, among these polymers of family (1), there may be mentioned:
- les copolymères d'acrylamide et de diméthylaminoéthyl méthacrylate quatemisé au sulfate de diméthyle ou avec un hologénure de diméthyle, tel que celui vendu sous la dénomination HERCOFLOC par la société HERCULES,- copolymers of acrylamide and of dimethylaminoethyl methacrylate quaternized with dimethyl sulphate or with a dimethyl hologenide, such as that sold under the name HERCOFLOC by the company HERCULES,
- les copolymères d'acrylamide et de chlorure de méthacryloyloxyéthyltriméthyl- ammonium décrits par exemple dans la demande de brevet EP-A-080976 et vendus sous la dénomination BINA QUAT P 100 par la société CIBA GEIGY,the copolymers of acrylamide and of methacryloyloxyethyltrimethylammonium chloride described for example in patent application EP-A-080976 and sold under the name BINA QUAT P 100 by the company CIBA GEIGY,
- le copolymère d'acrylamide et de méthosulfate de méthacryloyloxyéthyltriméthyl- ammonium vendu sous la dénomination RETEN par la société HERCULES,- the copolymer of acrylamide and methacryloyloxyethyltrimethylammonium ammonium methosulfate sold under the name RETEN by the company Hercules,
- les copolymères vinylpyrrolidone / acrylate ou méthacrylate de dialkylaminoalkyle quaternises ou non, tels que les produits vendus sous la dénomination "GAFQUAT" par la société ISP comme par exemple "GAFQUAT 734" ou "GAFQUAT 755" ou bien les produits dénommés "COPOLYMER 845, 958 et 937". Ces polymères sont décrits en détail dans les brevets français 2.077.143 et 2.393.573, - les terpolymères méthacrylate de diméthyl amino éthyle/ vinylcaprolactame/ vinylpyrrolidone tel que le produit vendu sous la dénomination GAFFIX VC 713 par la société ISP, - les copolymère vinylpyrrolidone / méthacrylamidopropyl dimethylamine commercialisés notamment sous la dénomination STYLEZE CC 10 par ISP,- vinylpyrrolidone / acrylate or methacrylate of dialkylaminoalkyl quaternized or not, such as the products sold under the name "GAFQUAT" by the company ISP such as for example "GAFQUAT 734" or "GAFQUAT 755" or else the products called "COPOLYMER 845, 958 and 937 ". These polymers are described in detail in French patents 2,077,143 and 2,393,573, - dimethyl amino ethyl methacrylate / vinylcaprolactam / vinylpyrrolidone terpolymers such as the product sold under the name GAFFIX VC 713 by the company ISP, - the vinylpyrrolidone / methacrylamidopropyl dimethylamine copolymer sold in particular under the name STYLEZE CC 10 by ISP,
- et les copolymères vinylpyrrolidone / méthacrylamide de diméthylaminopropyle quaternises tel que le produit vendu sous la dénomination "GAFQUAT HS 100" par la société ISP .- And vinylpyrrolidone / methacrylamide dimethylaminopropyl quaternized copolymers such as the product sold under the name "GAFQUAT HS 100" by the company ISP.
(2) Les dérivés d'éthers de cellulose comportant des groupements ammonium quaternaire décrits dans le brevet français 1 492 597, et en particulier les polymères commercialisés sous les dénominations "JR" (JR 400, JR 125, JR 30M) ou "LR" (LR 400, LR 30M) par la Société Union Carbide Corporation. Ces polymères sont également définis dans le dictionnaire CTFA comme des ammonium quaternaires d'hydroxyéthylcellulose ayant réagi avec un époxyde substitué par un groupement triméthylammonium .(2) Derivatives of cellulose ethers comprising quaternary ammonium groups described in French patent 1,492,597, and in particular the polymers marketed under the names "JR" (JR 400, JR 125, JR 30M) or "LR" (LR 400, LR 30M) by the Union Carbide Corporation. These polymers are also defined in the CTFA dictionary as quaternary ammoniums of hydroxyethylcellulose having reacted with an epoxide substituted by a trimethylammonium group.
(3) Les dérivés de cellulose cationiques tels que les copolymères de cellulose ou les dérivés de cellulose greffés avec un monomère hydrosoluble d'ammonium quaternaire, et décrits notamment dans le brevet US 4 131 576, tels que les hydroxyalkyl celluloses, comme les hydroxyméthyl-, hydroxyéthyl- ou hydroxypropyl celluloses greffées notamment avec un sel de méthacryloyléthyl triméthylammonium, de méthacrylmidopropyl triméthylammonium, de diméthyl- diallylammonium.(3) Cationic cellulose derivatives such as cellulose copolymers or cellulose derivatives grafted with a water-soluble quaternary ammonium monomer, and described in particular in US Pat. No. 4,131,576, such as hydroxyalkyl celluloses, such as hydroxymethyl- , hydroxyethyl- or hydroxypropyl celluloses grafted in particular with a salt of methacryloylethyl trimethylammonium, of methacrylmidopropyl trimethylammonium, of dimethyl-diallylammonium.
Les produits commercialisés répondant à cette définition sont plus particulièrement les produits vendus sous la dénomination "Celquat L 200" et "Celquat H 100" par la Société National Starch.The marketed products meeting this definition are more particularly the products sold under the name "Celquat L 200" and "Celquat H 100" by the National Starch Company.
(4) Les polysaccharides cationiques décrits plus particulièrement dans les brevets US 3 589 578 et 4 031 307 tel que les gommes de guar contenant des groupements cationiques trialkylammonium. On utilise par exemple des gommes de guar modifiées par un sel (par ex. chlorure) de 2,3-époxypropyl triméthylammonium.(4) The cationic polysaccharides described more particularly in US patents 3,589,578 and 4,031,307 such as guar gums containing cationic trialkylammonium groups. Guar gums modified with a salt (eg chloride) of 2,3-epoxypropyl trimethylammonium are used, for example.
De tels produits sont commercialisés notamment sous les dénominations commerciales de JAGUAR C13 S, JAGUAR C 15, JAGUAR C 17 ou JAGUAR C162 par la société MEYHALL. (5) Les polymères constitués de motifs pipérazinyle et de radicaux divalents alkylène ou hydroxyalkylène à chaînes droites ou ramifiées, éventuellement interrompues par des atomes d'oxygène, de soufre, d'azote ou par des cycles aromatiques ou hétérocycliques, ainsi que les produits d'oxydation et/ou de quatemisation de ces polymères. De tels polymères sont notamment décrits dans les brevets français 2.162.025 et 2.280.361.Such products are marketed in particular under the trade names of JAGUAR C13 S, JAGUAR C 15, JAGUAR C 17 or JAGUAR C162 by the company MEYHALL. (5) Polymers consisting of piperazinyl units and divalent alkylene or hydroxyalkylene radicals with straight or branched chains, optionally interrupted by oxygen, sulfur, nitrogen atoms or by aromatic or heterocyclic rings, as well as the products of oxidation and / or quaternization of these polymers. Such polymers are described in particular in French patents 2,162,025 and 2,280,361.
(6) Les polyaminoamides solubles dans l'eau préparés en particulier par polycondensation d'un composé acide avec une polyamine ; ces polyaminoamides peuvent être réticulés par une épihalohydrine, un diépoxyde, un dianhydride, un dianhydride non saturé, un dérivé bis-insaturé, une bis- halohyd ne, un bis-azétidinium, une bis-haloacyldiamine, un bis-halogénure d'alkyle ou encore par un oligomère résultant de la réaction d'un composé bifonctionnel réactif vis-à-vis d'une bis-halohydrine, d'un bis-azétidinium, d'une bis-haloacyldiamine, d'un bis-halogénure d'alkyle, d'une épilhalohydrine, d'un diépoxyde ou d'un dérivé bis-insaturé ; l'agent réticulant étant utilisé dans des proportions allant de 0,025 à 0,35 mole par groupement aminé du polyaminoamide ; ces polyaminoamides peuvent être alcoylés ou s'ils comportent une ou plusieurs fonctions aminés tertiaires, quaternisees. De tels polymères sont notamment décrits dans les brevets français 2.252.840 et 2.368.508 .(6) Water-soluble polyaminoamides prepared in particular by polycondensation of an acidic compound with a polyamine; these polyaminoamides can be crosslinked with an epihalohydrin, a diepoxide, a dianhydride, an unsaturated dianhydride, a bis-unsaturated derivative, a bis-halohydne, a bis-azetidinium, a bis-haloacyldiamine, a bis-halide of alkyl or also with an oligomer resulting from the reaction of a bifunctional compound reactive with a bis-halohydrin, a bis-azetidinium, a bis-haloacyldiamine, an alkyl bis-halide, an epilhalohydrin, a diepoxide or a bis-unsaturated derivative; the crosslinking agent being used in proportions ranging from 0.025 to 0.35 mole per amino group of the polyaminoamide; these polyaminoamides can be alkylated or if they contain one or more tertiary, quaternized amine functions. Such polymers are described in particular in French patents 2,252,840 and 2,368,508.
(7) Les dérivés de polyaminoamides résultant de la condensation de polyalcoylènes polyamines avec des acides polycarboxyliques suivie d'une alcoylation par des agents bifonctionnels. On peut citer par exemple les polymères acide adipique-diacoylaminohydroxyalcoyldialoylène triamine dans lesquels le radical alcoyle comporte de 1 à 4 atomes de carbone et désigne de préférence méthyle, éthyle, propyle. De tels polymères sont notamment décrits dans le brevet français 1.583.363. Parmi ces dérivés, on peut citer plus particulièrement les polymères acide adipique/diméthylaminohydroxypropyl/diéthylène triamine vendus sous la dénomination "Cartaretine F, F4 ou F8" par la société Sandoz. (8) Les polymères obtenus par réaction d'une polyalkylène polyamine comportant deux groupements aminé primaire et au moins un groupement aminé secondaire avec un acide dicarboxylique choisi parmi l'acide diglycolique et les acides dicarboxyliques aliphatiques saturés ayant de 3 à 8 atomes de carbone. Le rapport molaire entre le polyalkylène polylamine et l'acide dicarboxylique étant compris entre 0,8 : 1 et 1 ,4 : 1; le polyaminoamide en résultant étant amené à réagir avec l'épichlorhydrine dans un rapport molaire d'epichlorhydrine par rapport au groupement aminé secondaire du polyaminoamide compris entre 0,5 : 1 et 1 ,8 : 1. De tels polymères sont notamment décrits dans les brevets américains 3.227.615 et 2.961.347.(7) Polyaminoamide derivatives resulting from the condensation of polyalkylene polyamines with polycarboxylic acids followed by alkylation by bifunctional agents. Mention may be made, for example, of the adipic acid-diacoylaminohydroxyalkoyldialoylene triamine polymers in which the alkyl radical contains from 1 to 4 carbon atoms and preferably denotes methyl, ethyl, propyl. Such polymers are described in particular in French patent 1,583,363. Among these derivatives, there may be mentioned more particularly the adipic acid / dimethylaminohydroxypropyl / diethylene triamine polymers sold under the name "Cartaretine F, F4 or F8" by the company Sandoz. (8) The polymers obtained by reaction of a polyalkylene polyamine comprising two primary amine groups and at least one secondary amine group with a dicarboxylic acid chosen from diglycolic acid and saturated aliphatic dicarboxylic acids having from 3 to 8 carbon atoms. The molar ratio between the polyalkylene polylamine and the dicarboxylic acid being between 0.8: 1 and 1.4: 1; the resulting polyaminoamide being reacted with epichlorohydrin in a molar ratio of epichlorohydrin relative to the secondary amino group of the polyaminoamide of between 0.5: 1 and 1.8: 1. Such polymers are described in particular in the patents American 3,227,615 and 2,961,347.
Des polymères de ce type sont en particulier commercialisés sous la dénomination "Hercosett 57" par la société Hercules Inc. ou bien sous la dénomination de "PD 170" ou "Delsette 101" par la société Hercules dans le cas du copolymère d'acide adipique/époxypropyl/diéthylène-triamine.Polymers of this type are in particular sold under the name "Hercosett 57" by the company Hercules Inc. or else under the name of "PD 170" or "Delsette 101" by the company Hercules in the case of the adipic acid copolymer / epoxypropyl / diethylenetriamine.
(9) Les cyclopolymères d'alkyl diallyl aminé ou de dialkyl diallyl ammonium tels que les homopolymères ou copolymères comportant comme constituant principal de la chaîne des motifs répondant aux formules (V) ou (VI) :(9) Cyclopolymers of alkyl diallyl amine or dialkyl diallyl ammonium such as homopolymers or copolymers comprising, as main constituent of the chain, units corresponding to formulas (V) or (VI):
formules dans lesquelles k et t sont égaux à 0 ou 1 , la somme k + t étant égale à 1 ; R9 désigne un atome d'hydrogène ou un radical méthyle ; R et R8, indépendamment l'un de l'autre, désignent un groupement alkyle ayant de 1 à 22 atomes de carbone, un groupement hydroxyalkyle dans lequel le groupement alkyle a de préférence 1 à 5 atomes de carbone, un groupement amidoalkyle inférieur (C1-C4), ou R7 et Rg peuvent désigner conjointement avec l'atome d'azote auquel ils sont rattachés, des groupement hétérocycliques, tels que pipéridinyle ou morpholinyle ; R7 et Rg indépendamment l'un de l'autre désignent de préférence un groupement alkyle ayant de 1 à 4 atomes de carbone ; Y" est un anion tel que bromure, chlorure, acétate, borate, citrate, tartrate, bisulfate, bisulfite, sulfate, phosphate. Ces polymères sont notamment décrits dans le brevet français 2.080.759 et dans son certificat d'addition 2.190.406. Parmi les polymères définis ci-dessus, on peut citer plus particulièrement l'homopolymère de chlorure de diméthyldiallylammonium vendu sous la dénomination "Merquat 100" par la société Calgon (et ses homologues de faible masse moléculaire moyenne en poids) et les copolymères de chlorure de diallyldiméthylammonium et d'acrylamide commercialisés sous la dénomination "MERQUAT 550".formulas in which k and t are equal to 0 or 1, the sum k + t being equal to 1; R 9 denotes a hydrogen atom or a methyl radical; R and R 8 , independently of one another, denote an alkyl group having from 1 to 22 carbon atoms, a hydroxyalkyl group in which the alkyl group preferably has 1 to 5 carbon atoms, a lower amidoalkyl group (C1-C4), or R7 and Rg may denote jointly with the nitrogen atom to which they are attached , heterocyclic groups, such as piperidinyl or morpholinyl; R 7 and Rg, independently of one another, preferably denote an alkyl group having from 1 to 4 carbon atoms; Y " is an anion such as bromide, chloride, acetate, borate, citrate, tartrate, bisulfate, bisulfite, sulfate, phosphate. These polymers are described in particular in French patent 2,080,759 and in its certificate of addition 2,190,406. Among the polymers defined above, there may be mentioned more particularly the homopolymer of dimethyldiallylammonium chloride sold under the name "Merquat 100" by the company Calgon (and its low molecular weight average counterparts) and the chloride chloride copolymers diallyldimethylammonium and acrylamide marketed under the name "MERQUAT 550".
(10) Le polymère de diammonium quaternaire contenant des motifs récurrents répondant à la formule :(10) The quaternary diammonium polymer containing recurring units corresponding to the formula:
R10 R12 R 10 R 12
N+ -A, - (VII)N + -A, - (VII)
1 ' - N | +- B, η1 '- N | + - B, η -
R„ X" R13 X" formule (VII) dans laquelle :R „X" R 13 X " formula (VII) in which:
Rl0> Rl 1 > R12 et l 3> identiques ou différents, représentent des radicaux aliphatiques, alicycliques, ou arylaliphatiques contenant de 1 à 20 atomes de carbone ou des radicaux hydroxyalkylaliphatiques inférieurs, ou bien R-J Q. Rn > R-12 et R13, ensemble ou séparément, constituent avec les atomes d'azote auxquels ils sont rattachés des heterocycles contenant éventuellement un second hétéroatome autre que l'azote ou bien R-J O. 11. R12 e* R13 représentent un radical alkyle en C^ -CQ linéaire ou ramifié substitué par un groupement nitrile, ester, acyle, amide ou -CO-O- R14-D ou -CO-NH- R14-D où R14 est un alkylène et D un groupement ammonium quaternaire ; A1 et B1 représentent des groupements polyméthyléniques contenant de 2 à 20 atomes de carbone pouvant être linéaires ou ramifiés, saturés ou insaturés, et pouvant contenir, liés à ou intercalés dans la chaîne principale, un ou plusieurs cycles aromatiques, ou un ou plusieurs atomes d'oxygène, de soufre ou des groupements sulfoxyde, sulfone, disulfure, amino, alkylamino, hydroxyle, ammonium quaternaire, uréido, amide ou ester, et X" désigne un anion dérivé d'un acide minéral ou organique; A1 , Rio et R-|2 peuvent former avec les deux atomes d'azote auxquels ils sont rattachés un cycle pipérazinique ; en outre si A1 désigne un radical alkylène ou hydroxyalkylène linéaire ou ramifié, saturé ou insaturé, B1 peut également désigner un groupement -(CH2)n-CO-D-OC-(CH2)n- dans lequel D désigne : a) un reste de glycol de formule : -O-Z-O-, où Z désigne un radical hydrocarboné linéaire ou ramifié ou un groupement répondant à l'une des formules suivantes : -(CH2-CH2-O)x-CH2-CH2-Rl0 > Rl 1> R12 and l 3> identical or different, represent aliphatic, alicyclic, or arylaliphatic radicals containing from 1 to 20 carbon atoms or lower hydroxyalkylaliphatic radicals, or else RJ Q. Rn > R-12 and R13, together or separately, constitute with the nitrogen atoms to which they are attached heterocycles possibly containing a second heteroatom other than nitrogen or else RJ O. 11. R12 e * R13 represent a linear or branched C ^ -CQ alkyl radical substituted by a nitrile, ester, acyl, amide or -CO-O- R14-D or -CO-NH- R14-D group where R14 is an alkylene and D a quaternary ammonium group; A1 and B1 represent polymethylenic groups containing from 2 to 20 carbon atoms which may be linear or branched, saturated or unsaturated, and which may contain, linked to or intercalated in the main chain, one or more aromatic rings, or one or more atoms of oxygen, sulfur or sulfoxide, sulfone, disulfide, amino, alkylamino, hydroxyl, quaternary ammonium, ureido, amide or ester groups, and X " denotes an anion derived from a mineral or organic acid; A1, Rio and R- | 2 can form with the two nitrogen atoms to which they are attached a piperazine ring; in addition if A1 denotes a linear or branched, saturated or unsaturated alkylene or hydroxyalkylene radical, B1 can also denote a group - (CH2) n-CO -D-OC- (CH2) n- in which D denotes: a) a glycol residue of formula: -OZO-, where Z denotes a linear or branched hydrocarbon radical or a group corresponding to one of the following formulas: - (VS H2-CH 2 -O) x-CH2-CH 2 -
-[CH2-CH(CH3)-O]y-CH2-CH(CH3)- où x et y désignent un nombre entier de 1 à 4, représentant un degré de polymérisation défini et unique ou un nombre quelconque de 1 à 4 représentant un degré de polymérisation moyen ; b) un reste de diamine bis-secondaire tel qu'un dérivé de pipérazine ; c) un reste de diamine bis-primaire de formule : -NH-Y-NH-, où Y désigne un radical hydrocarboné linéaire ou ramifié, ou bien le radical bivalent- [CH 2 -CH (CH3) -O] y-CH 2 -CH (CH3) - where x and y denote an integer from 1 to 4, representing a defined and unique degree of polymerization or any number from 1 to 4 representing an average degree of polymerization; b) a bis-secondary diamine residue such as a piperazine derivative; c) a bis-primary diamine residue of formula: -NH-Y-NH-, where Y denotes a linear or branched hydrocarbon radical, or else the bivalent radical
-CH2-CH2-S-S-CH2-CH2- ; d) un groupement uréylène de formule : -NH-CO-NH- . De préférence, X~ est un anion tel que le chlorure ou le bromure.-CH2-CH2-S-S-CH2-CH2-; d) a ureylene group of formula: -NH-CO-NH-. Preferably, X ~ is an anion such as chloride or bromide.
Ces polymères ont une masse moléculaire moyenne en nombre généralement comprise entre 1000 et 100000.These polymers have a number average molecular weight generally between 1000 and 100,000.
Des polymères de ce type sont notamment décrits dans les brevets français 2.320.330, 2.270.846, 2.316.271 , 2.336.434 et 2.413.907 et les brevets US 2.273.780, 2.375.853, 2.388.614, 2.454.547, 3.206.462, 2.261.002, 2.271.378, 3.874.870, 4.001.432, 3.929.990, 3.966.904, 4.005.193, 4.025.617, 4.025.627, 4.025.653, 4.026.945 et 4.027.020. On peut utiliser plus particulièrement les polymères qui sont constitués de motifs récurrents répondant à la formule (VIII) suivante:Polymers of this type are described in particular in French patents 2,320,330, 2,270,846, 2,316,271, 2,336,434 and 2,413,907 and US patents 2,273,780, 2,375,853, 2,388,614, 2,454,547 , 3.206.462, 2.261.002, 2.271.378, 3.874.870, 4.001.432, 3.929.990, 3.966.904, 4.005.193, 4.025.617, 4.025.627, 4.025.653, 4.026.945 and 4.027 .020. It is possible to use more particularly the polymers which consist of recurring units corresponding to the following formula (VIII):
dans laquelle Rio, R11. R12 e* R13, identiques ou différents, désignent un radical alkyle ou hydroxyalkyle ayant de 1 à 4 atomes de carbone environ, n et p sont des nombres entiers variant de 2 à 20 environ et, X- est un anion dérivé d'un acide minéral ou organique. in which Rio, R 11. R 12 e * R 13, identical or different, denote an alkyl or hydroxyalkyl radical having from 1 to 4 carbon atoms approximately, n and p are whole numbers varying from 2 to 20 approximately and, X - is an anion derived from a mineral or organic acid.
(11) Les polymères de polyammonium quaternaire constitués de motifs de formule (IX) :(11) Quaternary polyammonium polymers consisting of units of formula (IX):
--
(IX) dans laquelle : p désigne un nombre entier variant de 1 à 6 environ, D peut être nul ou peut représenter un groupement — (CH2)r — O — dans lequel r désigne un nombre égal à 4 ou à 7, et X" est un anion dérivé d'un acide minéral ou organique.(IX) in which: p denotes an integer varying from 1 to 6 approximately, D can be zero or can represent a group - (CH2) r - O - in which r denotes a number equal to 4 or 7, and X " is an anion derived from a mineral or organic acid.
Les polymères cationiques comportant des motifs de formule (IX) sont notamment décrits dans la demande de brevet EP-A-122 324 et peuvent être préparés selon les procédés décrits dans les brevets U.S.A. n° 4 157 388, 4 390 689, 4 702 906, 4 719 282.The cationic polymers comprising units of formula (IX) are described in particular in patent application EP-A-122 324 and can be prepared according to the methods described in US patents No. 4,157,388, 4,390,689, 4,702,906 , 4,719,282.
Parmi ces polymères, on préfère ceux de masse moléculaire mesurée par RMN du Carbone 13 inférieure à 100000, et dans la formule de laquelle : p est égal à 3, et, a) D représente un groupement — (CH2k — CO — , X désigne un atome de chlore, la masse moléculaire mesurée par RMN du Carbone 13 ( RMN1 3C ) étant d'environ 5600 ; un polymère de ce type est proposé par la société MIRANOL sous le nom de MIRAPOL-AD1 , b) D représente un groupement — (CH2)7 — CO — , X désigne un atome de chlore, la masse moléculaire mesurée par RMN du Carbone 13 ( RMN^c ) étant d'environ 8100 ; un polymère de ce type est proposé par la société MIRANOL sous le nom de MIRAPOL-AZ1 , c) D désigne la valeur zéro, X désigne un atome de chlore, la masse moléculaire mesurée par RMN du Carbone 13, ( RMN1 3C ) étant d'environ 25500 ; un polymère de ce type est vendu par la société MIRANOL sous le nom MIRAPOL- A15, d) un " Block Copolymer " formé de motifs correspondant aux polymères décrits aux alinéas a) et c), proposé par la société MIRANOL sous les noms MIRAPOL-9, (masse moléculaire RMN^ 3C, environ 7800) MIRAPOL-175, (masse moléculaireAmong these polymers, those of molecular mass measured by NMR of Carbon 13 less than 100,000 are preferred, and in the formula of which: p is equal to 3, and, a) D represents a group - (CH2k - CO -, X denotes a chlorine atom, the molecular mass measured by NMR of Carbon 13 (NMR 1 3 C) being approximately 5600; a polymer of this type is proposed by company MIRANOL under the name of MIRAPOL-AD1, b) D represents a group - (CH2) 7 - CO -, X denotes a chlorine atom, the molecular mass measured by NMR of Carbon 13 (NMR ^ c) being approximately 8100; a polymer of this type is offered by the company MIRANOL under the name of MIRAPOL-AZ1, c) D denotes the value zero, X denotes a chlorine atom, the molecular mass measured by NMR of Carbon 13, (NMR 1 3 C) being about 25,500; a polymer of this type is sold by the company MIRANOL under the name MIRAPOL-A15, d) a "Block Copolymer" formed of units corresponding to the polymers described in paragraphs a) and c), offered by the company MIRANOL under the names MIRAPOL- 9, (RMN ^ 3 C molecular weight, about 7800) MIRAPOL-175, (molecular weight
RMN1 3C, environ 8000) MIRAPOL-95, (masse moléculaire RMN1 3C, environ 12500). 1 3 C NMR, about 8000) MIRAPOL-95, ( 1 3 C NMR molecular weight, about 12500).
Plus particulièrement encore, on préfère selon l'invention le polymère à motifs de formule (IX) dans laquelle p est égal à 3, D désigne la valeur zéro, X désigne un atome de chlore, la masse moléculaire mesurée par RMN du Carbone 13,More particularly still, according to the invention, the polymer with units of formula (IX) in which p is equal to 3 is preferred, D denotes the value zero, X denotes a chlorine atom, the molecular mass measured by NMR of Carbon 13,
( RMN1 3C ) étant d'environ 25500.(NMR 1 3 C) being approximately 25500.
(12) Les polymères quaternaires de vinylpyrrolidone et de vinylimidazole tels que par exemple les produits commercialisés sous les dénominations Luviquat FC 905, FC 550 et FC 370 par la société B.A.S.F.(12) Quaternary polymers of vinylpyrrolidone and of vinylimidazole such as for example the products marketed under the names Luviquat FC 905, FC 550 and FC 370 by the company B.A.S.F.
(13) Les polyamines comme le Polyquart H vendu par HENKEL, référencé sous le nom de " POLYETHYLENEGLYCOL (15) TALLOW POLYAMINE " dans le dictionnaire CTFA.(13) Polyamines such as Polyquart H sold by HENKEL, referenced under the name of "POLYETHYLENEGLYCOL (15) TALLOW POLYAMINE" in the CTFA dictionary.
(14) Les polymères réticulés de sels de méthacryloyioxyalkyl(Cι-C4) trialkyl(Cι- C4)ammonium tels que les polymères obtenus par homopolymérisation du diméthylaminoéthylméthacrylate quaternisé par le chlorure de méthyle, ou par copolymérisation de l'acrylamide avec le diméthylaminoéthylméthacrylate quaternisé par le chlorure de méthyle, l'homo ou la copolymérisation étant suivie d'une réticulation par un composé à insaturation oléfinique, en particulier le méthylène bis acrylamide. On peut plus particulièrement utiliser un copolymere réticulé acrylamide/chlorure de méthacryloyloxyéthyl triméthylammonium (20/80 en poids) sous forme de dispersion contenant 50 % en poids dudit copolymere dans de l'huile minérale. Cette dispersion est commercialisée sous le nom de(14) Crosslinked polymers of methacryloyioxyalkyl (Cι-C4) trialkyl (Cι- C4) ammonium salts such as the polymers obtained by homopolymerization of dimethylaminoethylmethacrylate quaternized with methyl chloride, or by copolymerization of acrylamide with dimethylaminoethylmethacrylate quaternized with methyl chloride, homo or copolymerization being followed by crosslinking with an olefinically unsaturated compound, in particular methylene bis acrylamide . One can more particularly use a crosslinked acrylamide / methacryloyloxyethyltrimethylammonium chloride copolymer (20/80 by weight) in the form of a dispersion containing 50% by weight of said copolymer in mineral oil. This dispersion is marketed under the name of
" SALCARE® SC 92 " par la Société ALLIED COLLOIDS. On peut également utiliser un homopolymère réticulé du chlorure de méthacryloyloxyéthyl triméthylammonium contenant environ 50 % en poids de l'homopolymère dans de l'huile minérale ou dans un ester liquide. Ces dispersions sont commercialisées sous les noms de " SALCARE® SC 95 " et " SALCARE® SC 96 " par la Société ALLIED COLLOIDS."SALCARE® SC 92" by the company ALLIED COLLOIDS. It is also possible to use a crosslinked homopolymer of methacryloyloxyethyl trimethylammonium chloride containing approximately 50% by weight of the homopolymer in mineral oil or in a liquid ester. These dispersions are marketed under the names of "SALCARE® SC 95" and "SALCARE® SC 96" by the company ALLIED COLLOIDS.
D'autres polymères cationiques utilisables dans le cadre de l'invention sont des polyalkylèneimines, en particulier des polyéthylèneimines, des polymères contenant des motifs vinylpyridine ou vinylpyridinium, des condensats de polyamines et d'epichlorhydrine, des polyuréylènes quaternaires et les dérivés de la chitine.Other cationic polymers which can be used in the context of the invention are polyalkyleneimines, in particular polyethyleneimines, polymers containing vinylpyridine or vinylpyridinium units, polyamine and epichlorohydrin condensates, quaternary polyuretylenes and chitin derivatives.
Parmi tous les polymères cationiques susceptibles d'être utilisés dans le cadre de la présente invention, on préfère mettre en oeuvre les polymères des familles (1), (9), (10) (11) et (14) et encore plus préférentiellement les polymères de formules (W) et (U) suivantes :Among all the cationic polymers capable of being used in the context of the present invention, it is preferred to use the polymers of families (1), (9), (10) (11) and (14) and even more preferably the polymers of formulas (W) and (U) below:
CH. CH.CH. CH.
-[- M*- (CH2)3 -N+- CH2)6 (W)- [- M * - (CH 2 ) 3 -N + - CH 2 ) 6 (W)
CI- ' "* | CI- CH3 CH3 et notamment ceux dont le poids moléculaire, déterminé par chromatographie par perméation de gel, est compris entre 9500 et 9900; CH . C2H5 CI- '"* | CI- CH 3 CH 3 and in particular those whose molecular weight, determined by gel permeation chromatography, is between 9500 and 9900; CH. C 2 H 5
i- N-- (CH2)3 -^+— CH2 ) 3 (U)i- N-- (CH 2 ) 3 - ^ + - CH 2 ) 3 (U)
Br I BrBr I Br
CH3 C2H5 et notamment ceux dont le poids moléculaire, déterminé par chromatographie par perméation de gel, est d'environ 1200.CH 3 C 2 H 5 and in particular those whose molecular weight, determined by gel permeation chromatography, is approximately 1200.
La concentration en polymère cationique dans les compositions selon la présente invention peut varier de 0,01 à 10% en poids par rapport au poids total de la composition, de préférence de 0,05 à 5% et plus préférentiellement encore de 0,1 à 3%.The concentration of cationic polymer in the compositions according to the present invention can vary from 0.01 to 10% by weight relative to the total weight of the composition, preferably from 0.05 to 5% and even more preferably from 0.1 to 3%.
Les polymères amphotères utilisables conformément à la présente invention peuvent être choisis parmi les polymères comportant des motifs K et M répartis statistiquement dans la chaîne polymère, où K désigne un motif dérivant d'un monomère comportant au moins un atome d'azote basique et M désigne un motif dérivant d'un monomère acide comportant un ou plusieurs groupements carboxyliques ou sulfoniques, ou bien K et M peuvent désigner des groupements dérivant de monomères zwittérioniques de carboxybétaïnes ou de sulfobétaïnes; K et M peuvent également désigner une chaîne polymère cationique comportant des groupements aminé primaire, secondaire, tertiaire ou quaternaire, dans laquelle au moins l'un des groupements aminé porte un groupement carboxylique ou sulfonique relié par l'intermédiaire d'un radical hydrocarboné, ou bien K et M font partie d'une chaîne d'un polymère à motif éthylène α,β-dicarboxylique dont l'un des groupements carboxyliques a été amené à réagir avec une polyamine comportant un ou plusieurs groupements aminé primaire ou secondaire.The amphoteric polymers which can be used in accordance with the present invention can be chosen from polymers comprising K and M units distributed statistically in the polymer chain, where K denotes a unit derived from a monomer comprising at least one basic nitrogen atom and M denotes a unit deriving from an acid monomer comprising one or more carboxylic or sulphonic groups, or else K and M may denote groups deriving from zwitterionic monomers of carboxybetaines or of sulphobetaines; K and M can also denote a cationic polymer chain comprising primary, secondary, tertiary or quaternary amine groups, in which at least one of the amine groups carries a carboxylic or sulphonic group linked via a hydrocarbon radical, or although K and M form part of a chain of a polymer with an α, β-dicarboxylic ethylene unit, one of the carboxyl groups of which has been reacted with a polyamine comprising one or more primary or secondary amine groups.
Les polymères filmogènes amphotères répondant à la définition donnée ci-dessus plus particulièrement préférés sont choisis parmi les polymères suivants :The amphoteric film-forming polymers corresponding to the definition given above which are more particularly preferred are chosen from the following polymers:
(1) Les polymères résultant de la copolymérisation d'un monomère dérivé d'un composé vinylique portant un groupement carboxylique tel que plus particulièrement l'acide acrylique, l'acide méthacrylique, l'acide maléique, l'acide alpha-chloracrylique, et d'un monomère basique dérivé d'un composé vinylique substitué contenant au moins un atome basique tel que plus particulièrement les dialkylaminoalkylméthacrylate et acrylate, les dialkylaminoalkylméthacrylamide et acrylamide. De tels composés sont décrits dans le brevet américain n° 3 836 537. On peut également citer le copolymere acrylate de sodium / chlorure d'acrylamidopropyl trimethyl ammonium vendu sous la dénomination POLYQUART KE 3033 par la Société HENKEL.(1) The polymers resulting from the copolymerization of a monomer derived from a vinyl compound carrying a carboxylic group such as more particularly acrylic acid, methacrylic acid, maleic acid, alpha-chloroacrylic acid, and of a basic monomer derived of a substituted vinyl compound containing at least one basic atom such as more particularly the dialkylaminoalkylmethacrylate and acrylate, the dialkylaminoalkylmethacrylamide and acrylamide. Such compounds are described in US Pat. No. 3,836,537. Mention may also be made of the sodium acrylate / acrylamide propyl trimethyl ammonium chloride copolymer sold under the name POLYQUART KE 3033 by the company HENKEL.
Le composé vinylique peut être également un sel de dialkyldiallylammonium tel que le chlorure de diméthyldiallylammonium. Les copolymères d'acide acrylique et de ce dernier monomère sont proposés sous les appelationsThe vinyl compound can also be a dialkyldiallylammonium salt such as dimethyldiallylammonium chloride. Copolymers of acrylic acid and of the latter monomer are available under the names
MERQUAT 280, MERQUAT 295 et MERQUAT PLUS 3330 par la société CALGON.MERQUAT 280, MERQUAT 295 and MERQUAT PLUS 3330 by the company CALGON.
(2) Les polymères comportant des motifs dérivant : a) d'au moins un monomère choisi parmi les acrylamides ou les méthacrylamides substitués sur l'azote par un radical alkyle, b) d'au moins un comonomère acide contenant un ou plusieurs groupements carboxyliques réactifs, et c) d'au moins un comonomère basique tel que des esters à substituants aminé primaire, secondaire, tertiaire et quaternaire des acides acrylique et méthacrylique et le produit de quaternisation du méthacrylate de diméthylaminoéthyle avec le sulfate de diméthyle ou diéthyle.(2) Polymers comprising units derived from: a) at least one monomer chosen from acrylamides or methacrylamides substituted on nitrogen by an alkyl radical, b) from at least one acidic comonomer containing one or more carboxylic groups reactants, and c) at least one basic comonomer such as esters with primary, secondary, tertiary and quaternary amine substituents of acrylic and methacrylic acids and the quaternization product of dimethylaminoethyl methacrylate with dimethyl or diethyl sulfate.
Les acrylamides ou méthacrylamides N-substitués plus particulièrement préférés selon l'invention sont les groupements dont les radicaux alkyle contiennent de 2 à 12 atomes de carbone et plus particulièrement le N-éthylacrylamide, le N- tertiobutyl-acrylamide, le N-tertiooctyl-acrylamide, le N-octylacrylamide, le N- décylacrylamide, le N-dodécylacrylamide ainsi que les méthacrylamides correspondants.The N-substituted acrylamides or methacrylamides more particularly preferred according to the invention are the groups in which the alkyl radicals contain from 2 to 12 carbon atoms and more particularly N-ethylacrylamide, N-tertiobutyl-acrylamide, N-tertiooctyl-acrylamide , N-octylacrylamide, N-decylacrylamide, N-dodecylacrylamide and the corresponding methacrylamides.
Les comonomères acides sont choisis plus particulièrement parmi les acides acrylique, méthacrylique, crotonique, itaconique, maléique, fumarique ainsi que les monoesters d'alkyle ayant 1 à 4 atomes de carbone des acides ou des anhydrides maléique ou fumarique. Les comonomères basiques préférés sont des méthacrylates d'aminoéthyle, de butyl aminoéthyle, de N,N'-diméthylaminoéthyle, de N-tertio-butylaminoéthyle. On utilise particulièrement les copolymères dont la dénomination CTFA (4ème Ed., 1991) est Octylacrylamide/acrylates/butylaminoethylmethacrylate copolymer tels que les produits vendus sous la dénomination AMPHOMER ou LOVOCRYL 47 par la société NATIONAL STARCH.The acid comonomers are chosen more particularly from acrylic, methacrylic, crotonic, itaconic, maleic, fumaric acids as well as alkyl monoesters having 1 to 4 carbon atoms of maleic or fumaric acids or anhydrides. The preferred basic comonomers are aminoethyl, butyl aminoethyl, N, N'-dimethylaminoethyl, N-tert-butylaminoethyl methacrylates. Copolymers are particularly used whose name CTFA (4th Ed., 1991) is Octylacrylamide / acrylates / butylaminoethylmethacrylate copolymer such as the products sold under the name AMPHOMER or LOVOCRYL 47 by the company NATIONAL STARCH.
(3) Les polyaminoamides réticulés et alcoylés partiellement ou totalement dérivant de polyaminoamides de formule générale :(3) Crosslinked and alkylated polyaminoamides partially or totally derived from polyaminoamides of general formula:
-^ CO — R19 - CO — Z — ]- (X)- ^ CO - R 19 - CO - Z -] - (X)
dans laquelle R-j g représente un radical divalent dérivé d'un acide dicarboxylique saturé, d'un acide aliphatique mono ou dicarboxylique à double liaison éthylénique, d'un ester d'un alcanol inférieur ayant 1 à 6 atomes de carbone de ces acides ou d'un radical dérivant de l'addition de l'un quelconque desdits acides avec une aminé bis primaire ou bis secondaire, et Z désigne un radical d'une polyalkylene-polyamine bis-primaire, mono ou bis-secondaire et de préférence représente : a) dans les proportions de 60 à 100 moles %, le radicalin which Rj g represents a divalent radical derived from a saturated dicarboxylic acid, from a mono or dicarboxylic acid with ethylene double bond, from an ester of a lower alkanol having 1 to 6 carbon atoms of these acids or d 'a radical derived from the addition of any one of said acids with a primary bis or secondary bis amino, and Z denotes a radical of a bis-primary, mono or bis-secondary polyalkylene polyamine and preferably represents: a ) in the proportions of 60 to 100 mol%, the radical
où x=2 et p=2 ou 3, ou bien x=3 et p=2 ce radical dérivant de la diéthylène triamine, de la triéthylène tétraamine ou de la dipropylène triamine; b) dans les proportions de 0 à 40 moles % le radical (XI) ci-dessus, dans lequel x=2 et p=1 et qui dérive de l'éthylènediamine, ou le radical dérivant de la pipérazine :where x = 2 and p = 2 or 3, or else x = 3 and p = 2 this radical deriving from diethylene triamine, triethylene tetraamine or dipropylene triamine; b) in the proportions of 0 to 40 mol% the radical (XI) above, in which x = 2 and p = 1 and which derives from ethylenediamine, or the radical deriving from piperazine:
\ / c) dans les proportions de 0 à 20 moles % le radical -NH-(CH2)6-NH- dérivant de l'hexaméthylènediamine, ces polyaminoamines étant réticulées par addition d'un agent réticulant bifonctionnel choisi parmi les épihalohydrines, les diépoxydes, les dianhydrides, les dérivés bis insaturés, au moyen de 0,025 à 0,35 mole d'agent réticulant par groupement aminé du polyaminoamide et alcoylés par action d'acide acrylique, d'acide chloracétique ou d'une alcane sultone ou de leurs sels. Les acides carboxyliques saturés sont choisis de préférence parmi les acides ayant 6 à 10 atomes de carbone tels que l'acide adipique, triméthyl-2,2,4-adipique et triméthyl-2,4,4-adipique, téréphtalique, les acides à double liaison éthylénique comme par exemple les acides acrylique, méthacrylique, itaconique.\ / c) in the proportions of 0 to 20 mol% of the radical -NH- (CH2) 6-NH- deriving from hexamethylenediamine, these polyaminoamines being crosslinked by addition of a bifunctional crosslinking agent chosen from epihalohydrins, diepoxides, dianhydrides, bis unsaturated derivatives, using 0.025 to 0.35 mole of crosslinking agent by amino group of the polyaminoamide and alkylated by the action of acrylic acid, chloracetic acid or an alkane sultone or their salts. The saturated carboxylic acids are preferably chosen from acids having 6 to 10 carbon atoms such as adipic, trimethyl-2,2,4-adipic acid and trimethyl-2,4,4-adipic, terephthalic acid, ethylenic double bond such as for example acrylic, methacrylic, itaconic acids.
Les alcanes sultones utilisées dans l'alcoylation sont de préférence la propane ou la butane sultone, les sels des agents d'alcoylation sont de préférence les sels de sodium ou de potassium.The alkane sultones used in the alkylation are preferably propane or butane sultone, the salts of the alkylating agents are preferably the sodium or potassium salts.
(4) Les polymères comportant des motifs zwittérioniques de formule :(4) Polymers comprising zwitterionic units of formula:
dans laquelle R20 désigne un groupement insaturé polymérisable tel qu'un groupement acrylate, méthacrylate, acrylamide ou méthacrylamide, y et z représentent un nombre entier de 1 à 3, R21 et R22 représentent un atome d'hydrogène, méthyle, éthyle ou propyle, R23 et R24 représentent un. atome d'hydrogène ou un radical alkyle de telle façon que la somme des atomes de carbone dans R23 et R24 ne dépasse pas 10. Les polymères comprenant de telles unités peuvent également comporter des motifs dérivés de monomères non zwittérioniques tels que l'acrylate ou le méthacrylate de diméthyl ou diéthylaminoéthyle ou des alkyle acryiates ou méthacrylates, des acrylamides ou méthacrylamides ou l'acétate de vinyle.in which R20 denotes a polymerizable unsaturated group such as an acrylate, methacrylate, acrylamide or methacrylamide group, y and z represent an integer from 1 to 3, R21 and R22 represent a hydrogen, methyl, ethyl or propyl atom, R23 and R24 represent one. hydrogen atom or an alkyl radical such that the sum of the carbon atoms in R23 and R24 does not exceed 10. The polymers comprising such units may also contain units derived from non-zwitterionic monomers such as acrylate or dimethyl or diethylaminoethyl methacrylate or alkyl acrylates or methacrylates, acrylamides or methacrylamides or vinyl acetate.
A titre d'exemple, on peut citer le copolymere de méthacrylate de méthyle / diméthyl-carboxyméthylammonio-éthylméthacrylate de méthyle tel que le produit vendu sous la dénomination DIAFORMER Z301 par la société SANDOZ.By way of example, there may be mentioned the copolymer of methyl methacrylate / methyl dimethyl-carboxymethylammonio-ethyl methacrylate such as the product sold under the name DIAFORMER Z301 by the company SANDOZ.
(5) les polymères dérivés du chitosane comportant des motifs monomères répondant aux formules (XIII), (XIV), (XV) suivantes : °-(5) polymers derived from chitosan comprising monomer units corresponding to formulas (XIII), (XIV), (XV) below: ° -
R^-COOHR ^ -COOH
(XIII) (XIV)(XIII) (XIV)
(XV)(XV)
le motif (XIII) étant présent dans des proportions comprises entre 0 et 30%, le motif (XIV) dans des proportions comprises entre 5 et 50% et le motif F dans des proportions comprises entre 30 et 90%, étant entendu que dans ce motif (XV), R25 représente un radical de formule :the motif (XIII) being present in proportions of between 0 and 30%, the motif (XIV) in proportions of between 5 and 50% and the motif F in proportions of between 30 and 90%, it being understood that in this unit (XV), R 25 represents a radical of formula:
R 27 R 28 26 C — (0)q - C-R 27 R 28 26 C - (0) q - C-
dans laquelle si q=0, R26, 27 et 28- identiques ou différents, représentent chacun un atome d'hydrogène, un reste méthyle, hydroxyle, acétoxy ou amino, un reste monoalcoyiamine ou un reste dialcoyiamine éventuellement interrompus par un ou plusieurs atomes d'azote et/ou éventuellement substitués par un ou plusieurs groupes aminé, hydroxyle, carboxyle, alcoylthio, sulfonique, un reste alcoylthio dont le groupe aicoyle porte un reste amino, l'un au moins des radicaux R2 , R27 et R28 étant dans ce cas un atome d'hydrogène ; ou si q=1 , R26> R27 et R28 représentent chacun un atome d'hydrogène, ainsi que les sels formés par ces composés avec des bases ou des acides.in which if q = 0, R26, 27 and 28- identical or different, each represent a hydrogen atom, a methyl, hydroxyl, acetoxy or amino residue, a monoalkoyiamine residue or a dialkoyiamine residue optionally interrupted by one or more atoms of nitrogen and / or optionally substituted by one or more amino, hydroxyl, carboxyl, alkylthio or sulfonic groups, an alkylthio residue in which the aicoyl group carries an amino residue, at least one of the radicals R2, R27 and R28 being in this case a hydrogen atom; or if q = 1, R26 > R27 and R28 each represent a hydrogen atom, as well as the salts formed by these compounds with bases or acids.
(6) Les polymères dérivés de la N-carboxyalkylation du chitosane comme le N-carboxyméthyl chitosane ou le N-carboxybutyl chitosane vendu sous la dénomination "EVALSAN" par la société JAN DEKKER.(6) Polymers derived from the N-carboxyalkylation of chitosan such as N-carboxymethyl chitosan or N-carboxybutyl chitosan sold under the name "EVALSAN" by the company JAN DEKKER.
(7) Les polymères répondant à la formule générale (XI) tels que ceux décrits par exemple dans le brevet français 1 400 366 : dans laquelle R29 représente un atome d'hydrogène, un radical CH3O, CH3CH2O, phényle, R30 désigne l'hydrogène ou un radical alkyle inférieur tel que méthyle, éthyle, R3idésigne l'hydrogène ou un radical alkyle inférieur tel que méthyle, éthyle, R32 désigne un radical alkyle inférieur tel que méthyle, éthyle ou un radical répondant à la formule : -R33-N(R3i)2, R33 représentant un groupement -CH2-CH2- , -CH2-CH2-CH2- , -CH2-CH(CH3)- , R31 ayant les significations mentionnées ci-dessus, ainsi que les homologues supérieurs de ces radicaux et contenant jusqu'à 6 atomes de carbone.(7) The polymers corresponding to the general formula (XI) such as those described for example in French patent 1,400,366: in which R29 represents a hydrogen atom, a CH3O radical, CH3CH2O, phenyl, R30 denotes hydrogen or a lower alkyl radical such as methyl, ethyl, R3 denotes hydrogen or a lower alkyl radical such as methyl, ethyl, R32 denotes a lower alkyl radical such as methyl, ethyl or a radical corresponding to the formula: -R33-N (R3i) 2, R33 representing a group -CH2-CH2-, -CH2-CH2-CH2-, -CH2-CH ( CH3) -, R31 having the meanings mentioned above, as well as the higher homologs of these radicals and containing up to 6 carbon atoms.
(8) Des polymères amphotères du type -D-X-D-X- choisis parmi: a) les polymères obtenus par action de l'acide chloracétique ou le chloracétate de sodium sur les composés comportant au moins un motif de formule :(8) Amphoteric polymers of the type -D-X-D-X- chosen from: a) the polymers obtained by the action of chloracetic acid or sodium chloroacetate on the compounds comprising at least one unit of formula:
-D-X-D-X-D- (XVII) où D désigne un radical-D-X-D-X-D- (XVII) where D denotes a radical
\ / et X désigne le symbole E ou E', E ou E' identiques ou différents désignent un radical bivalent qui est un radical alkylène à chaîne droite ou ramifiée comportant jusqu'à 7 atomes de carbone dans la chaîne principale non substituée ou substituée par des groupements hydroxyle et pouvant comporter en outre des atomes d'oxygène, d'azote, de soufre, 1 à 3 cycles aromatiques et/ou hétérocycliques; les atomes d'oxygène, d'azote et de soufre étant présents sous forme de groupements éther, thioéther, sulfoxyde, sulfone, sulfonium, alkylamine, alkénylamine, des groupements hydroxyle, benzylamine, oxyde d'aminé, ammonium quaternaire, amide, imide, alcool, ester et/ou uréthanne ;\ / and X denotes the symbol E or E ', E or E', which are identical or different, denote a bivalent radical which is an alkylene radical with a straight or branched chain containing up to 7 carbon atoms in the unsubstituted main chain or substituted by hydroxyl groups and which may also contain oxygen, nitrogen, sulfur atoms, 1 to 3 aromatic and / or heterocyclic rings; the oxygen, nitrogen and sulfur atoms being present in the form of ether, thioether, sulfoxide, sulfone, sulfonium, alkylamine, alkenylamine groups, hydroxyl groups, benzylamine, amine oxide, quaternary ammonium, amide, imide, alcohol, ester and / or urethane;
b) les polymères de formule :b) polymers of formula:
-D-X-D-X- (XVIII) où D désigne un radical-D-X-D-X- (XVIII) where D denotes a radical
\\
N-NOT-
\ / et X désigne le symbole E ou E' et au moins une fois E'; E ayant la signification indiquée ci-dessus et E' est un radical bivalent qui est un radical alkylène à chaîne droite ou ramifiée ayant jusqu'à 7 atomes de carbone dans la chaîne principale, substitué ou non par un ou plusieurs radicaux hydroxyle et comportanf un ou plusieurs atomes d'azote, l'atome d'azote étant substitué par une chaîne alkyle interrompue éventuellement par un atome d'oxygène et comportant obligatoirement une ou plusieurs fonctions carboxyle ou une ou plusieurs fonctions hydroxyle et bétaïnisées par réaction avec l'acide chloracétique ou du chloracétate de soude.\ / and X denotes the symbol E or E 'and at least once E'; E having the meaning indicated above and E 'is a bivalent radical which is a straight or branched chain alkylene radical having up to 7 carbon atoms in the main chain, substituted or not by one or more hydroxyl radicals and comprising a or more nitrogen atoms, the nitrogen atom being substituted by an alkyl chain optionally interrupted by an oxygen atom and necessarily having one or more carboxyl functions or one or more hydroxyl functions and betainized by reaction with chloracetic acid or sodium chloracetate.
(9) Les copolymères alkyl(Cι-C5)vinyléther / anhydride maléique modifié partiellement par semiamidification avec une N,N-dialkylaminoalkylamine telle que la N,N-diméthylaminopropylamine ou par semiestérification avec une N,N-dialcanolamine. Ces copolymères peuvent également comporter d'autres comonomères vinyliques tels que le vinylcaprolactame.(9) Alkyl (Cι-C5) vinyl ether / maleic anhydride copolymers partially modified by semiamidification with an N, N-dialkylaminoalkylamine such as N, N-dimethylaminopropylamine or by semiesterification with an N, N-dialcanolamine. These copolymers can also contain other vinyl comonomers such as vinylcaprolactam.
Les polymères amphotères particulièrement préférés selon l'invention sont ceux de la famille (1). Selon l'invention, le ou les polymères amphotères peuvent représenter de 0,01 % à 10 % en poids, de préférence de 0,05 % à 5 % en poids, et encore plus préférentiellement de 0,1 % à 3 % en poids, du poids total de la composition.The amphoteric polymers which are particularly preferred according to the invention are those of the family (1). According to the invention, the amphoteric polymer (s) can represent from 0.01% to 10% by weight, preferably from 0.05% to 5% by weight, and even more preferably from 0.1% to 3% by weight , of the total weight of the composition.
Les compositions de l'invention comprennent de préférence un ou plusieurs tensioactifs.The compositions of the invention preferably comprise one or more surfactants.
Le ou les tensioactifs peuvent être indifféremment choisis, seuls ou en mélanges, au sein des tensioactifs anioniques, amphotères, non ioniques, zwittérioniques et cationiques.The surfactant (s) can be chosen either, alone or as a mixture, from anionic, amphoteric, nonionic, zwitterionic and cationic surfactants.
Les tensioactifs convenant à la mise en oeuvre de la présente invention sont notamment les suivants :The surfactants which are suitable for carrying out the present invention are in particular the following:
(i) Tensioactif(s) anionique(s) :(i) Anionic surfactant (s):
A titre d'exemple de tensio-actifs anioniques utilisables, seuls ou mélanges, dans le cadre de la présente invention, on peut citer notamment (liste non limitative) les sels (en particulier sels alcalins, notamment de sodium, sels d'ammonium, sels d'aminés, sels d'aminoalcools ou sels de magnésium) des composés suivants : les alkylsulfates, les alkyléthersulfates, alkylamidoéthersulfates, alkylarylpolyéthersulfates, monoglycérides sulfates ; les alkylsulfonates, alkylphosphates, alkylamidesulfonates, alkylarylsulfonates, α-oléfine-sulfonates, paraffine-sulfonates ; les alkyl(Cβ-C2 ) sulfosuccinates, les alkyl(C6-C2 ) éthersulfosuccinates, les alkyl(C6-C24) amidesulfosuccinates ; les alkyl(C6-C2 ) sulfoacétates ; les acy!(C6-C2 ) sarcosinates et les acyI(Cβ-C2 ) glutamates. On peut également utiliser les esters d'alkyl(C6-C2 )polyglycosides carboxyliques tels que les alkylglucoside citrates, les alkylpolyglycoside tartrate et les alkylpolyglycoside sulfosuccinates., les alkylsulfosuccinamat.es ; les acyliséthionates et les N-acyltau rates, le radical alkyle ou acyle de tous ces différents composés comportant de préférence de 12 à 20 atomes de carbone, et le radical aryle désignant de préférence un groupement phényle ou benzyle. Parmi les tensioactifs anioniques encore utilisables, on peut également citer les sels d'acides gras tels que les sels des acides oléique, ricinoléique, palmitique, stéarique, les acides d'huile de coprah ou d'huile de coprah hydrogénée ; les acyl- lactylates dont le radical acyle comporte 8 à 20 atomes de carbone. On peut également utiliser les acides d'alkyl D galactoside uroniques et leurs sels, les acides alkyl(C6-C24) éther carboxyliques polyoxyalkylénés, les acides alkyl(C6- C2 )aryl éther carboxyliques polyoxyalkylénés, les acides alkyl(C6-C24) amido éther carboxyliques polyoxyalkylénés et leurs sels, en particulier ceux comportant de 2 à 50 groupements oxyde d'alkylène en particulier d'éthylène, et leurs mélanges.By way of example of anionic surfactants which can be used, alone or as mixtures, in the context of the present invention, there may be mentioned in particular (non-limiting list) the salts (in particular alkaline salts, in particular sodium salts, ammonium salts, amine salts, amino alcohol salts or magnesium salts) of the following compounds: alkylsulphates, alkylethersulphates, alkylamidoethersulphates, alkylarylpolyethersulphates, monoglycerides sulphates; alkylsulfonates, alkylphosphates, alkylamidesulfonates, alkylarylsulfonates, α-olefin-sulfonates, paraffin-sulfonates; alkyl (Cβ-C 2 ) sulfosuccinates, alkyl (C 6 -C 2 ) ethersulfosuccinates, alkyl (C 6 -C 24 ) amidesulfosuccinates; (C 6 -C 2 ) alkyl sulfoacetates; acy! (C 6 -C 2 ) sarcosinates and acyI (Cβ-C 2 ) glutamates. It is also possible to use the alkyl esters (C6-C 2 ) carboxylic polyglycosides such as the alkylglucoside citrates, the alkylpolyglycoside tartrate and the alkylpolyglycoside sulfosuccinates., The alkylsulfosuccinamates; acylisethionates and N-acyltau spleens, the alkyl or acyl radical of all these different compounds preferably containing from 12 to 20 carbon atoms, and the aryl radical preferably denoting a phenyl or benzyl group. Among the anionic surfactants which can still be used, mention may also be made of the salts of fatty acids such as the salts of oleic, ricinoleic and palmitic acids, stearic acid from coconut oil or hydrogenated coconut oil; acyl lactylates whose acyl radical contains 8 to 20 carbon atoms. It is also possible to use the alkyl D galactoside uronic acids and their salts, the polyoxyalkylenated (C 6 -C 24 ) alkyl ether carboxylic acids, the polyoxyalkylenated (C 6 - C 2 ) aryl ether carboxylic acids, the alkyl (C 6 -C 24 ) polyoxyalkylenated carboxylic amido ether and their salts, in particular those comprising from 2 to 50 alkylene oxide groups, in particular ethylene, and their mixtures.
(ii) Tensioactif(s) non ionique(s) :(ii) Nonionic surfactant (s):
Les agents tensioactifs non-ioniques sont, eux aussi, des composés bien connus en soi (voir notamment à cet égard "Handbook of Surfactants" par M.R. PORTER, éditions Blackie & Son (Glasgow and London), 1991 , pp 116-178) et leur nature ne revêt pas, dans le cadre de la présente invention, de caractère critique. Ainsi, ils peuvent être notamment choisis parmi (liste non limitative) les alcools, les alpha-diols, les alkylphénols polyéthoxylés, polypropoxylés, ayant une chaîne grasse comportant par exemple 8 à 18 atomes de carbone, le nombre de groupements oxyde d'éthylène ou oxyde de propylène pouvant aller notamment de 2 à 50. On peut également citer les copolymères d'oxyde d'éthylène et de propylène, les condensats d'oxyde d'éthylène et de propylène sur des alcools gras ; les amides gras polyéthoxylés ayant de préférence de 2 à 30 moles d'oxyde d'éthylène, les amides gras polyglycérolés comportant en moyenne 1 à 5 groupements glycérol et en particulier 1 ,5 à 4 ; les esters d'acides gras du sorbitan oxyéthylénés ayant de 2 à 30 moles d'oxyde d'éthylène ; les esters d'acides gras du sucrose, les esters d'acides gras du polyéthylèneglycol, les alkylpolyglycosides, les dérivés de N-alkyl glucamine, les oxydes d'aminés tels que les oxydes d'alkyl (C-I Q-C 4) aminés ou les oxydes de N- acylaminopropylmorpholine. On notera que les alkylpolyglycosides constituent des tensio-actifs non-ioniques rentrant particulièrement bien dans le cadre de la présente invention.Non-ionic surfactants are also well known compounds per se (see in particular in this regard "Handbook of Surfactants" by MR PORTER, Blackie & Son editions (Glasgow and London), 1991, pp 116-178) and their nature is not, in the context of the present invention, critical. Thus, they can in particular be chosen from (nonlimiting list) alcohols, alpha-diols, polyethoxylated, polypropoxylated alkylphenols, having a fatty chain comprising for example 8 to 18 carbon atoms, the number of ethylene oxide groups or propylene oxide which can range in particular from 2 to 50. Mention may also be made of copolymers of ethylene oxide and of propylene, condensates of ethylene oxide and of propylene on fatty alcohols; polyethoxylated fatty amides preferably having from 2 to 30 moles of ethylene oxide, polyglycerolated fatty amides comprising on average 1 to 5 glycerol groups and in particular 1, 5 to 4; esters of oxyethylenated sorbitan fatty acids having from 2 to 30 moles of ethylene oxide; sucrose fatty acid esters, polyethylene glycol fatty acid esters, alkylpolyglycosides, N-alkyl glucamine derivatives, amine oxides such as alkyl oxides (CI QC 4) amines or oxides of N-acylaminopropylmorpholine. It will be noted that the alkylpolyglycosides constitute nonionic surfactants which are particularly well suited to the present invention.
(iii) Tensioactif(s) amphotère(s) ou zwittérionique(s : Les agents tensioactifs amphotères ou zwittérioniques, dont la nature ne revêt pas dans le cadre de la présente invention de caractère critique, peuvent être notamment (liste non limitative) des dérivés d'aminés secondaires ou tertiaires aliphatiques, dans lesquels le radical aliphatique est une chaîne linéaire ou ramifiée comportant 8 à 18 atomes de carbone et contenant au moins un groupe anionique hydrosolubilisant (par exemple carboxylate, sulfonate, sulfate, phosphate ou phosphonate) ; on peut citer encore les alkyl (C8-C20) bétaïnes, les sulfobétaïnes, les alkyl (C8-C20) amidoalkyl (C -CQ) bétaïnes ou les alkyl (Cβ- C20) amidoalkyl (C1-C5) sulfobétaïnes.(iii) Amphoteric or zwitterionic surfactant (s): Amphoteric or zwitterionic surfactants, the nature of which is not critical in the context of the present invention, may in particular be (non-limiting list) derivatives of aliphatic secondary or tertiary amines, in which the aliphatic radical is a chain linear or branched having 8 to 18 carbon atoms and containing at least one water-soluble anionic group (for example carboxylate, sulfonate, sulfate, phosphate or phosphonate); mention may also be made of (C8-C20) alkyl betaines, sulfobetaines, (C8-C20) alkyl amidoalkyl (C -CQ) betaines or (Cβ-C20) amidoalkyl (C1-C5) sulfobetaines alkyl.
Parmi les dérivés d'aminés, on peut citer les produits vendus sous la dénomination MIRANOL, tels que décrits dans les brevets US-2 528 378 et US-2 781 354 et classés dans le dictionnaire CTFA, 3ème édition, 1982, sous les dénominations Amphocarboxyglycinates et Amphocarboxypropionates de structures respectives :Among the amine derivatives, mention may be made of the products sold under the name Miranol, as described in patents US-2,528,378 and US-2,781,354 and classified in the CTFA dictionary, 3rd edition, 1982, under the names Amphocarboxyglycinates and Amphocarboxypropionates of respective structures:
R34 -CONHCH2CH2 -N(R35)(R36)(CH2COO-) dans laquelle : R34 désigne un radical alkyle d'un acide R34-COOH présent dans l'huile de coprah hydrolysée, un radical heptyle, nonyle ou undécyle, R35 désigne un groupement bêta-hydroxyéthyle et R35 un groupement carboxyméthyle ; et R34'-CONHCH2CH2-N(B)(C) dans laquelle :R34 -CONHCH 2 CH 2 -N (R35) (R36) (CH 2 COO-) in which: R34 denotes an alkyl radical of an acid R34-COOH present in hydrolyzed coconut oil, a heptyl, nonyl or undecyl, R35 denotes a beta-hydroxyethyl group and R35 denotes a carboxymethyl group; and R 3 4'-CONHCH 2 CH2-N (B) (C) in which:
B représente -CH2CH2OX', C représente -(CH2)Z -Y', avec z = 1 ou 2, X' désigne le groupement -CH2CH2-COOH ou un atome d'hydrogène Y' désigne -COOH ou le radical -CH2 - CHOH - SO3HB represents -CH2CH2OX ', C represents - (CH2) Z -Y', with z = 1 or 2, X 'denotes the group -CH2CH2-COOH or a hydrogen atom Y' denotes -COOH or the radical -CH 2 - CHOH - SO3H
R34' désigne un radical alkyle d'un acide R37 -COOH présent dans l'huile de coprah ou dans l'huile de lin hydrolysée, un radical alkyle, notamment en C7, Cg, C-j 1 ou C-13, un radical alkyle en C-17 et sa forme iso, un radical C-J7 insaturé. Ces composés sont classés dans le dictionnaire CTFA, 5ème édition, 1993, sous les dénominations Disodium Cocoamphodiacetate, Disodium Lauroampho- diacetate, Disodium Caprylamphodiacetate, Disodium Capryloamphodiacetate, Disodium Cocoamphodipropionate, Disodium Lauroamphodipropionate, Disodium Caprylamphodipropionate, Disodium Capryloamphodipropionate, . Lauroampho- dipropionic acid, Cocoamphodipropionic acid.R34 ′ denotes an alkyl radical of an acid R37 -COOH present in coconut oil or in hydrolyzed linseed oil, an alkyl radical, in particular C7, Cg, Cj 1 or C-13, an alkyl radical in C-17 and its iso form, an unsaturated C-J7 radical. These compounds are classified in the CTFA dictionary, 5th edition, 1993, under the names Disodium Cocoamphodiacetate, Disodium Lauroampho- diacetate, Disodium Caprylamphodiacetate, Disodium Capryloamphodiacetate, Disodium Cocoamphodipropionate, Disodium Lauroamphodipropionate, Disodium Capryl. Lauroampho- dipropionic acid, Cocoamphodipropionic acid.
A titre d'exemple on peut citer le cocoamphodiacetate commercialisé sous la dénomination commerciale MIRANOL® C2M concentré par la société RHODIA CHIMIE.By way of example, mention may be made of the cocoamphodiacetate sold under the trade name MIRANOL® C2M concentrated by the company RHODIA CHIMIE.
(iv) Tensioactifs cationiques :(iv) Cationic surfactants:
Parmi les tensioactifs cationiques on peut citer en particulier (liste non limitative) : les sels d'aminés grasses primaires, secondaires ou tertiaires, éventuellement polyoxyalkylénées ; les sels d'ammonium quaternaire tels que les chlorures ou les bromures de tétraalkylammonium, d'alkylamidoalkyltrialkylammonium, de trialkylbenzylammonium, de trialkylhydroxyalkyl-ammonium ou d'alkylpyridinium; les dérivés d'imidazoline ; ou les oxydes d'aminés à caractère cationique.Among the cationic surfactants that may be mentioned in particular (nonlimiting list): the salts of primary, secondary or tertiary fatty amines, optionally polyoxyalkylenated; quaternary ammonium salts such as chlorides or bromides of tetraalkylammonium, alkylamidoalkyltrialkylammonium, trialkylbenzylammonium, trialkylhydroxyalkylammonium or alkylpyridinium; imidazoline derivatives; or amine oxides of a cationic nature.
Les quantités d'agents tensioactifs présents dans la composition prête à l'emploi selon l'invention peuvent varier de 0,01 à 40% et de préférence de 0,1 à 30% du poids total de la composition.The amounts of surfactants present in the ready-to-use composition according to the invention can vary from 0.01 to 40% and preferably from 0.1 to 30% of the total weight of the composition.
Les compositions selon l'invention peuvent également contenir d'autres agents d'ajustement de la rhéologie tels que les épaississants cellulosiquesThe compositions according to the invention may also contain other rheology adjusting agents such as cellulosic thickeners
(hydroxyéthycellulose, hydroxypropylcellulose, carboxyméthylcellulose..), la gomme de guar et ses dérivés( hydroxypropylguar..), les gommes d'origine microbienne (gomme de xanthane, gomme de scléroglucane..), les épaississants synthétiques tels que les homopolymères réticulés d'acide acrylique ou d'acide acrylamidopropanesulfonique et les polymères associatifs ioniques ou non ioniques tels que les polymères commercialisés sous les appellations PEMULEN TR1 ou TR2 par la société GOODRICH, SALCARE SC90 par la société ALLIED COLLOIDS, ACULYN 22, 28, 33, 44, ou 46 par la société ROHM & HAAS et ELFACOS T210 et T212 par la société AKZO.(hydroxyethylcellulose, hydroxypropylcellulose, carboxymethylcellulose, etc.), guar gum and its derivatives (hydroxypropylguar, etc.), gums of microbial origin (xanthan gum, scleroglucan gum, etc.), synthetic thickeners such as crosslinked homopolymers of acrylic acid or acrylamidopropanesulfonic acid and ionic or nonionic associative polymers such as polymers sold under the names Pemulen TR1 or TR2 by the company Goodrich, Salcare SC90 by the company ALLIED COLLOIDS, ACULYN 22, 28, 33, 44, or 46 by the company ROHM & HAAS and ELFACOS T210 and T212 by the company AKZO.
Ces épaississants d'appoint peuvent représenter de 0,05 à 10% en poids du poids total de la composition.These additional thickeners can represent from 0.05 to 10% by weight of the total weight of the composition.
Les compositions selon l'invention contiennent en outre avantageusement un agent alcalin.The compositions according to the invention also advantageously contain an alkaline agent.
Parmi les agents alcalinisants on peut citer, à titre d'exemple, l'ammoniaque, le chlorure d'ammonium, les carbonates alcalins ou alcalino-terreux, les silicates alcalins ou alcalino-terreux, les phosphates alcalins ou alcalino-terreux, les alcanolamines telles que les mono-, di- et triéthanolamines ainsi que leurs dérivés, les hydroxydes de sodium ou de potassium et les composés de formule (XIX) suivante :Among the basifying agents, there may be mentioned, by way of example, ammonia, ammonium chloride, alkali or alkaline earth carbonates, alkali or alkaline earth silicates, alkaline or alkaline earth phosphates, alkanolamines such as mono-, di- and triethanolamines as well as their derivatives, sodium or potassium hydroxides and the compounds of formula (XIX) below:
dans laquelle R est un reste propylène éventuellement substitué par un groupement hydroxyle ou un radical alkyle en C-ι-C ; R38, R39, R4o et R4ι, identiques ou différents, .représentent un atome d'hydrogène, un radical alkyle en Cι-C4 ou hydroxyalkyle en C-ι-C .wherein R is a propylene residue optionally substituted by a hydroxyl group or a C-ι-C alkyl radical; R 38 , R 39 , R 4 o and R 4 ι, identical or different,. Represent a hydrogen atom, an alkyl radical in Cι-C 4 or hydroxyalkyl in C-ι-C.
Les compositions de l'invention peuvent également contenir des agents séquestrants comme par exemple l'acide éthylènediamine tétraacétique (EDTA).The compositions of the invention can also contain sequestering agents such as for example ethylenediamine tetraacetic acid (EDTA).
Lorsque les compositions contenant l'agent oxydant et le polymère à squelette aminoplaste-éther sont sous forme anhydre ( poudre ou crème ), elles contiennent les agents principaux et additifs mentionnés ci-dessus sous forme de solides ou de liquides essentiellement anhydres. Elles peuvent également contenir des charges minérales ou organiques telles que la silice ou les argiles. Elles peuvent aussi contenir des liants tels que la vinylpyrrolidone, les huiles ou les cires, les polyalkylèneglycols ou les dérivés de polyalkylèneglycols. Elles peuvent aussi contenir des lubrifiants comme les stéarates de polyol ou les stérates de métaux alcalins ou alcalino-terreux, ainsi que des agents colorants ou matifiants comme les oxydes de titane.When the compositions containing the oxidizing agent and the polymer with an aminoplast-ether skeleton are in anhydrous form (powder or cream), they contain the main agents and additives mentioned above in the form of essentially anhydrous solids or liquids. They can also contain mineral or organic fillers such as silica or clays. They can also contain binders such as vinylpyrrolidone, oils or waxes, polyalkylene glycols or derivatives of polyalkylene glycols. They may also contain lubricants such as polyol stearates or alkali or alkaline earth metal sterates, as well as coloring or matifying agents such as titanium oxides.
Lorsque le milieu contenant l'agent oxydant est un milieu aqueux, il peut éventuellement contenir des solvants organiques acceptables sur le plan cosmétique, dont plus particulièrement, des alcools tels que l'alcool éthylique, l'alcool isopropylique, l'alcool benzylique, et l'alcool phényléthylique, ou des glycols ou éthers de glycol tels que, par exemple, les éthers monométhylique, monoéthylique et monobutylique d'ethyleneglycol, le propyleneglycol ou ses éthers tels que, par exemple, le monométhyléther de propyleneglycol, le butylèneglycol, le dipropylèneglycol ainsi que les alkyléthers de diéthylèneglycol comme par exemple, le monoéthyléther ou le monobutyléther du diéthylèneglycol, dans des concentrations comprises entre environ 0,5 et 20% et, de préférence, entre environ 2 et 10% en poids par rapport au poids total de la composition.When the medium containing the oxidizing agent is an aqueous medium, it may optionally contain cosmetically acceptable organic solvents, including more particularly, alcohols such as ethyl alcohol, isopropyl alcohol, benzyl alcohol, and phenylethyl alcohol, or glycols or glycol ethers such as, for example, monomethyl, monoethyl and monobutyl ethers of ethyleneglycol, propyleneglycol or its ethers such as, for example, propylene glycol monomethyl ether, butylene glycol, dipropylene glycol as well as the diethylene glycol alkyl ethers such as, for example, the monoethyl ether or the monobutyl ether of diethylene glycol, in concentrations of between approximately 0.5 and 20% and, preferably, between approximately 2 and 10% by weight relative to the total weight of the composition.
La composition de décoloration selon l'invention encore contenir une quantité efficace d'autres agents, par ailleurs antérieurement connus en décoloration, tels que divers adjuvants usuels comme des silicones volatiles ou non, cycliques ou linéaires ou ramifiées, organomodifiées (notamment par des groupements aminés) ou non organomodifiées, des conservateurs, des céramides, des cires ou des huiles, végétales, minérales ou synthétiques, des acides et en particuliers des AH A etc..The bleaching composition according to the invention also contains an effective amount of other agents, which have previously been known in bleaching, such as various usual adjuvants such as volatile or non-volatile, cyclic or linear or branched, organomodified silicones (in particular by amino groups ) or not organomodified, preservatives, ceramides, waxes or oils, vegetable, mineral or synthetic, acids and in particular HA A etc.
Bien entendu, l'homme de l'art veillera à choisir le ou les éventuels composés complémentaires mentionnés ci-avant, de manière telle que les propriétés avantageuses attachées intrinsèquement à la composition de décoloration selon l'invention ne soient pas, ou substantiellement pas, altérées par la ou les adjonctions envisagées.Of course, those skilled in the art will take care to choose the optional compound (s) mentioned above, so that the advantageous properties intrinsically attached to the bleaching composition according to the invention are not, or not substantially, altered by the planned addition (s).
Le pH de la composition prête à l'emploi est généralement compris entre les valeurs 4 et 12. Il est de préférence compris entre 7 et 11 ,5 et encore plus préférentiellement entre 8 et 11. De préférence, le procédé de décoloration selon l'invention consiste à appliquer la composition oxydante prête à l'emploi, sur les fibres kératiniques sèches ou humides, et à la laisser agir pendant un temps de pause variant, de préférence, de 1 à 60 minutes environ, et plus préférentiellement de 10 à 45 minutes environ, à rincer les fibres, puis éventuellement à les laver au shampooing, puis à les rincer à nouveau, et à les sécher.The pH of the ready-to-use composition is generally between the values 4 and 12. It is preferably between 7 and 11, 5 and even more preferably between 8 and 11. Preferably, the bleaching process according to the invention consists in applying the ready-to-use oxidizing composition to the dry or wet keratin fibers, and to leaving it to act for a pause time varying, preferably, from 1 to 60 minutes approximately, and more preferably 10 to 45 minutes approximately, to rinse the fibers, then optionally to wash them in shampoo, then to rinse them again, and to dry them.
Des exemples concrets illustrant l'invention sont indiqués ci-après, sans pour autant présenter un caractère limitatif.Concrete examples illustrating the invention are indicated below, without however being limiting in nature.
EXEMPLE 1 :EXAMPLE 1:
On a préparé la composition de décoloration aqueuse prête à l'emploi suivante (exprimée en grammes):The following ready-to-use aqueous bleaching composition was prepared (expressed in grams):
MA*= Matière ActiveMA * = Active Matter
La composition de décoloration ci-dessus a été appliquée et laissée 45 minutes sous casque sur des cheveux naturels, puis rincée abondamment à l'eau. On a obtenu un éclaircissement régulier de la chevelure. EXEMPLE 2 :The above bleaching composition was applied and left for 45 minutes under a helmet on natural hair, then rinsed thoroughly with water. We obtained a regular lightening of the hair. EXAMPLE 2:
On a préparé la composition de décoloration suivante (exprimée en grammes):The following bleaching composition was prepared (expressed in grams):
40 g de la composition anhydre ci-dessus ont été mélangés avec 80 g de la composition aqueuse suivante :40 g of the above anhydrous composition were mixed with 80 g of the following aqueous composition:
On a obtenu alors une crème décolorante prête à l'emploi qui, appliquée et laissée 45 minutes sous casque, a permis d'obtenir une décoloration puissante et homogène de cheveux naturels foncés. A ready-to-use bleaching cream was then obtained which, applied and left for 45 minutes under a helmet, made it possible to obtain a powerful and uniform bleaching of dark natural hair.

Claims

REVENDICATIONS
1. Composition prête à l'emploi pour la décoloration des fibres kératiniques, en particulier des fibres kératiniques humaines telles que les cheveux, comprenant, dans un milieu approprié pour la décoloration, au moins un agent oxydant, caractérisée par le fait qu'elle contient en outre au moins un polymère épaississant à squelette aminoplaste-éther.1. Ready-to-use composition for bleaching keratin fibers, in particular human keratin fibers such as the hair, comprising, in a medium suitable for bleaching, at least one oxidizing agent, characterized in that it contains in addition at least one thickening polymer with an aminoplast-ether skeleton.
2. Composition selon la revendication 1 , caractérisée par le fait que le ou les polymères aminoplaste-éther sont choisis parmi ceux contenant au moins un motif de structure (I) suivante :2. Composition according to Claim 1, characterized in that the aminoplast-ether polymer (s) are chosen from those containing at least one unit of structure (I) below:
dans laquelle : -AMP est un résidu aminoplaste avec unités alkylènes,in which: -AMP is an aminoplast residue with alkylene units,
-R désigne un atome d'hydrogène, un radical alkyl C-1C4 ou un radical acyle-R denotes a hydrogen atom, a C-1C4 alkyl radical or an acyl radical
C1 C4,C1 C4,
-RO-i est un résidu alkylèneoxy divalent,-RO-i is a divalent alkyleneoxy residue,
-p désigne un nombre entier positif, le ou les groupements OR étant liés aux unités alkylènes du résidu AMP.-p denotes a positive integer, the OR group or groups being linked to the alkylene units of the AMP residue.
3. Composition selon les revendications 1 ou 2, caractérisée par le fait que le ou les polymères à squelette aminoplaste-éther sont choisis parmi ceux contenant au moins un motif de structure (II) suivante :3. Composition according to claims 1 or 2, characterized in that the polymer or polymers with an aminoplast-ether skeleton are chosen from those containing at least one unit of structure (II) below:
dans laquelle -AMP, R, RO-| et p ont la même signification que dans la revendication 2, in which -AMP, R, RO- | and p have the same meaning as in claim 2,
- RO2 est un groupe hydrophobe différent de RO lié à AMP via un hétéroatome et comprenant au moins deux atomes de carbone, et, -q est un nombre entier positif.- RO2 is a hydrophobic group different from RO linked to AMP via a heteroatom and comprising at least two carbon atoms, and, -q is a positive integer.
4. Composition selon la revendication 3, caractérisée par le fait que le ou les polymères aminoplaste-éther sont choisis parmi les polymères de structure (III) ou (lllbis) suivantes :4. Composition according to Claim 3, characterized in that the aminoplast-ether polymer (s) are chosen from the following polymers of structure (III) or (IIIb):
R2- l lbis) R2- l lbis)
dans lesquelles :in which :
AMP, R, RO-| , RO2, p et q ont la même signification que dans les revendicationsAMP, R, RO- | , RO2, p and q have the same meaning as in the claims
2 et 3,2 and 3,
R2 ou R3, identiques ou différents représentent un groupe terminal pouvant désigner un atome d'hydrogène, un groupement RO-| H, un groupement RO2H, un groupement AMP(OR)p ou tout groupement monofonctionnel tel que alkyle, cycloalkyle, aryle, aralkyle, alkylaryle, alkyloxyalkyle, aryloxyalkyle, cycloalkoxyalkyle, a étant un nombre plus grand que 1 et de préférence plus grand que 2.R2 or R3, identical or different, represent a terminal group which can denote a hydrogen atom, a group RO- | H, a RO2H group, an AMP (OR) p group or any monofunctional group such as alkyl, cycloalkyl, aryl, aralkyl, alkylaryl, alkyloxyalkyl, aryloxyalkyl, cycloalkoxyalkyl, a being a number greater than 1 and preferably greater than 2 .
5. Composition selon l'une quelconque des revendications 2 à 4, caractérisée par le fait que les résidus aminoplastes porteurs de leurs groupements OR sont choisis parmi ceux de structures (IV) à (XV) suivantes : 5. Composition according to any one of claims 2 to 4, characterized in that the aminoplast residues carrying their OR groups are chosen from those of structures (IV) to (XV) below:
R ayant la même signification que dans la revendication 2, R1 désigne alkyle C1C4, y est un nombre au moins égal à 2, x désigne 0 ou 1.R having the same meaning as in claim 2, R1 denotes C1C4 alkyl, y is a number at least equal to 2, x denotes 0 or 1.
6. Composition selon l'une quelconque des revendications 2 à 4, caractérisée par le fait que les résidus aminoplastes porteurs de leurs groupements OR sont choisis parmi ceux de structure (XVI) suivante :6. Composition according to any one of claims 2 to 4, characterized in that the aminoplast residues carrying their OR groups are chosen from those of structure (XVI) below:
dans laquelle R, p , et x ont les mêmes significations que dans les revendications 2 et 5. in which R, p, and x have the same meanings as in claims 2 and 5.
7. Composition selon l'une quelconque des revendications 2 à 6, caractérisée par le fait que les résidus alkylèneoxy sont ceux correspondants aux diols de formule générale (XVII) suivante :7. Composition according to any one of claims 2 to 6, characterized in that the alkyleneoxy residues are those corresponding to the diols of general formula (XVII) below:
HO-(ZO)y-(Z1(Z2O)w)t-(Z'O)y'-Z3OH (XVII), y et y' étant des nombres allant de 0 à 1000, t et w étant des nombres allant de 0 à 10, Z, Z', Z2 et Z3 sont des radicaux alkylène en C2C4 et de préférence des radicauxHO- (ZO) y- (Z1 (Z2O) w) t- (Z'O) y'-Z3OH (XVII), y and y 'being numbers ranging from 0 to 1000, t and w being numbers ranging from 0 to 10, Z, Z ', Z2 and Z3 are C2C4 alkylene radicals and preferably radicals
-CH2-CH(Z4)- et -CH2-CH(Z4)-CH2-, Z1 étant un radical linéaire ou cyclique, ramifié ou non, aromatique ou non, comportant ou non un ou plusieurs heteroatomes et possédant de 1 à 40 atomes de carbone, Z4 désignant un atome d'hydrogène ou un radical alkyle en C1 C4 ou un radical acyle en C1 C3 étant entendu qu'au moins un des radicaux Z4 des radicaux Z, Z',-CH2-CH (Z4) - and -CH2-CH (Z4) -CH2-, Z1 being a linear or cyclic radical, branched or not, aromatic or not, comprising or not one or more heteroatoms and having from 1 to 40 carbon atoms, Z4 denoting a hydrogen atom or a C1 C4 alkyl radical or a radical C1 C3 acyl, it being understood that at least one of the radicals Z4 of the radicals Z, Z ',
Z2 et Z3 est différent de acyle.Z2 and Z3 is different from acyl.
8. Composition selon la revendication 7, caractérisée par le fait que le radical Z4 désigne un atome d' hydrogène ou un radical méthyle.8. Composition according to Claim 7, characterized in that the radical Z4 denotes a hydrogen atom or a methyl radical.
9. Composition selon les revendications 7 et 8, caractérisée par le fait que t=0 et que Z, Z' et Z3 désignent -CH2CH2- , l'un au moins de y ou y' étant différent de O.9. Composition according to Claims 7 and 8, characterized in that t = 0 and that Z, Z 'and Z3 denote -CH2CH2-, at least one of y or y' being different from O.
10. Composition selon l'une quelconque des revendications précédentes, caractérisée par le fait que les polymères à squelette aminoplaste-éther sont choisis parmi les produits suivants :10. Composition according to any one of the preceding claims, characterized in that the polymers with an aminoplast-ether skeleton are chosen from the following products:
PEG-180/Octoxynol-40/TMMG Copolymer, PEG-180/Laureth-50/TMMG Copolymer, Polyether-1.PEG-180 / Octoxynol-40 / TMMG Copolymer, PEG-180 / Laureth-50 / TMMG Copolymer, Polyether-1.
11. Composition selon l'une quelconque des revendications 1 à 10, caractérisée par le fait que les polymères à squelette aminoplaste-éther sont utilisés en une quantité pouvant varier de 0,01 à 10% en poids du poids total de la composition.11. Composition according to any one of claims 1 to 10, characterized in that the polymers with an aminoplast-ether skeleton are used in an amount which can vary from 0.01 to 10% by weight of the total weight of the composition.
12. Composition selon la revendication 11 , caractérisée par le fait que les polymères à squelette aminoplaste-éther sont utilisés en une quantité pouvant varier de 0,1 à 5% en poids du poids total de la composition.12. Composition according to claim 11, characterized in that the polymers with an aminoplast-ether skeleton are used in an amount which can vary from 0.1 to 5% by weight of the total weight of the composition.
13. Composition selon l'une quelconque des revendications précédentes, caractérisée par le fait que le ou les agents oxydants sont choisis parmi le peroxyde d'hydrogène et les composés libérant du peroxyde d'hydrogène par hydrolyse tels que le peroxyde d'urée et les persels, les chlorites, les systèmes enzymatiques générateurs d'espèces oxydantes et les peroxydes organiques.13. Composition according to any one of the preceding claims, characterized in that the oxidizing agent or agents are chosen from hydrogen peroxide and the compounds releasing hydrogen peroxide by hydrolysis such as urea peroxide and persalts, chlorites, enzymatic systems generating oxidizing species and organic peroxides.
14. Composition selon la revendication 13, caractérisée par le fait que le persel est un persulfate ou un perborate de métal alcalin ou alcalino-terreux.14. Composition according to claim 13, characterized in that the persalt is a persulfate or a perborate of alkali or alkaline earth metal.
15. Composition selon la revendication 13, caractérisée par le fait que le système enzymatique est une oxydoreductase à deux électrons associée à son donneur en présence d'air.15. Composition according to claim 13, characterized in that the enzymatic system is an oxidoreductase with two electrons associated with its donor in the presence of air.
16. Composition selon la revendication 15, caractérisée par le fait que l'oxydoréductase est l'uricase et son donneur l'acide urique.16. Composition according to claim 15, characterized in that the oxidoreductase is uricase and its donor uric acid.
17. Composition selon la revendication 13, caractérisée par le fait que la concentration en peroxyde d'hydrogène varie de 2 à 40 volumes.17. Composition according to claim 13, characterized in that the concentration of hydrogen peroxide varies from 2 to 40 volumes.
18. Composition selon la revendication 13, caractérisée par le fait que la concentration en composés oxydants peut varier de 0,1 à 25 % en poids par rapport au poids total de la composition.18. Composition according to Claim 13, characterized in that the concentration of oxidizing compounds can vary from 0.1 to 25% by weight relative to the total weight of the composition.
19. Composition selon l'une quelconque des revendications précédentes, caractérisée par le fait qu'elle contient en outre des colorants directs.19. Composition according to any one of the preceding claims, characterized in that it also contains direct dyes.
20. Composition selon l'une quelconque des revendications précédentes, caractérisée par le fait qu'elle contient en outre au moins un polymère cationique ou amphotère.20. Composition according to any one of the preceding claims, characterized in that it also contains at least one cationic or amphoteric polymer.
21. Composition selon la revendication 20, caractérisée par le fait que le polymère cationique est un polymère de polyammonium quaternaire constitué de motifs récurrents répondant à la formule (W) suivante : CH . CH,21. Composition according to Claim 20, characterized in that the cationic polymer is a quaternary polyammonium polymer consisting of recurring units corresponding to the following formula (W): CH. CH,
{- N±- (CH2)3 -N+— (CH2)6 (W) cι- | Cr CH, CH3 {- N ± - (CH 2 ) 3 -N + - (CH 2 ) 6 (W) cι- | Cr CH, CH 3
22. Composition selon la revendication 20, caractérisée par le fait que le polymère cationique est un polymère de polyammonium quaternaire constitué de motifs récurrents répondant à la formule (U) suivante :22. Composition according to Claim 20, characterized in that the cationic polymer is a quaternary polyammonium polymer consisting of recurring units corresponding to the following formula (U):
CH3 C2H5 CH 3 C 2 H 5
-E- N^- (CH2)3-N+— (CH2)3 (U)-E- N ^ - (CH 2 ) 3 -N + - (CH 2 ) 3 (U)
Br i BrBr i Br
CH3 C2H5 CH 3 C 2 H 5
23. Composition selon la revendication 20, caractérisée par le fait que le polymère amphotère est un copolymere comprenant au moins comme monomères de l'acide acrylique et un sel de diméthyldiallylammonium.23. Composition according to claim 20, characterized in that the amphoteric polymer is a copolymer comprising at least as monomers of acrylic acid and a dimethyldiallylammonium salt.
24. Composition selon l'une quelconque des revendications 20 à 23, caractérisée par le fait que le ou les polymères cationiques ou amphotères représentent de 0,01 % à 10 %, de préférence de 0,05 % à 5 %, et encore plus préférentiellement de 0,1 % à 3 % en poids, du poids total de la composition.24. Composition according to any one of claims 20 to 23, characterized in that the cationic or amphoteric polymer (s) represent from 0.01% to 10%, preferably from 0.05% to 5%, and even more preferably from 0.1% to 3% by weight, of the total weight of the composition.
25. Composition selon l'une quelconque des revendications précédentes, caractérisée par le fait qu'elle contient au moins un tensioactif choisi parmi les tensioactifs anioniques, cationiques, non ioniques ou amphotères.25. Composition according to any one of the preceding claims, characterized in that it contains at least one surfactant chosen from anionic, cationic, nonionic or amphoteric surfactants.
26. Composition selon la revendication 25, caractérisée par le fait que les tensioactifs représentent 0,01 à 40% et de préférence de 0,1 à 30% en poids, du poids total de la composition. 26. Composition according to Claim 25, characterized in that the surfactants represent 0.01 to 40% and preferably from 0.1 to 30% by weight, of the total weight of the composition.
27. Composition selon l'une quelconque des revendications précédentes, caractérisée par le fait qu'elle contient au moins un agent épaississant additionnel.27. Composition according to any one of the preceding claims, characterized in that it contains at least one additional thickening agent.
28. Composition selon la revendication 27 , caractérisée par le fait que l'agent épaississant additionnel est un dérivé de cellulose, un dérivé de guar, une gomme d'origine microbienne, un épaississant synthétique.28. Composition according to claim 27, characterized in that the additional thickening agent is a cellulose derivative, a guar derivative, a gum of microbial origin, a synthetic thickener.
29. Composition selon les revendications 27-28, caractérisée par le fait que le ou les agents épaississants additionnels représentent 0,05 à 10% en poids du poids total de la composition.29. Composition according to claims 27-28, characterized in that the additional thickening agent (s) represent 0.05 to 10% by weight of the total weight of the composition.
30. Composition selon l'une quelconque des revendications précédentes, caractérisée par le fait qu'elle contient en outre au moins un agent alcalin dans des quantités allant de 0,05 à 30% en poids du poids total de la composition.30. Composition according to any one of the preceding claims, characterized in that it also contains at least one alkaline agent in amounts ranging from 0.05 to 30% by weight of the total weight of the composition.
31. Composition selon la revendication 30 , caractérisée par le fait que l'agent alcalinisant est choisi parmi, l'ammoniaque, le chlorure d'ammonium, les carbonates alcalins ou alcalino-terreux, les silicates alcalins ou alcalino-terreux, les phosphates alcalins ou alcalino-terreux, les alcanolamines telles que les mono- , di- et triéthanolamines ainsi que leurs dérivés, les hydroxydes de sodium ou de potassium et les composés de formule (XIX) suivante :31. Composition according to claim 30, characterized in that the basifying agent is chosen from, ammonia, ammonium chloride, alkali or alkaline earth carbonates, alkali or alkaline earth silicates, alkaline phosphates or alkaline-earth, alkanolamines such as mono-, di- and triethanolamines as well as their derivatives, sodium or potassium hydroxides and the compounds of formula (XIX) below:
R 38 \ . R 40R 38 \. R 40
N - R - N (XIX)N - R - N (XIX)
R39-" ^ R41R 39 - "^ R 41
dans laquelle R est un reste propylène éventuellement substitué par un groupement hydroxyle ou un radical alkyle en Cι-C4 ; R38, R39, R40 et R41, identiques ou différents, représentent un atome d'hydrogène, un radical alkyle en C C ou hydroxyalkyle en C C4.in which R is a propylene residue optionally substituted by a hydroxyl group or a Cι-C 4 alkyl radical; R 38 , R 39 , R 40 and R 41 , which may be identical or different, represent a hydrogen atom, a CC 4 alkyl radical or a CC 4 hydroxyalkyl radical.
32. Composition selon l'une quelconque des revendications 1 à 31 , caractérisée par le fait qu'elle est obtenue par mélange extemporané au moment de l'emploi d'une composition anhydre contenant au moins un agent oxydant et d'au moins une composition aqueuse, l'une au moins des compositions anhydre ou aqueuse contenant au moins un polymère à squelette aminoplaste-éther.32. Composition according to any one of claims 1 to 31, characterized in that it is obtained by extemporaneous mixing at the time of use an anhydrous composition containing at least one oxidizing agent and at least one aqueous composition, at least one of the anhydrous or aqueous compositions containing at least one polymer with an aminoplast-ether backbone.
33. Composition selon la revendication 32, caractérisée par le fait que la composition anhydre est sous forme pulvérulente.33. Composition according to claim 32, characterized in that the anhydrous composition is in pulverulent form.
34. Composition selon les revendications 32-33, caractérisée par le fait que la composition anhydre contient au moins un additif choisi parmi les charges minérales ou organiques telles que la silice ou les argiles, les liants tels que la vinylpyrrolidone, les huiles ou les cires, les polyalkylèneglycols ou les dérivés de polyalkylèneglycols, les lubrifiants comme les stéarates de polyol ou les stéarates de métaux alcalins ou alcalino-terreux et les agents colorants ou matifiants comme les oxydes de titane.34. Composition according to claims 32-33, characterized in that the anhydrous composition contains at least one additive chosen from mineral or organic fillers such as silica or clays, binders such as vinylpyrrolidone, oils or waxes , polyalkylene glycols or derivatives of polyalkylene glycols, lubricants such as polyol stearates or stearates of alkali or alkaline earth metals and coloring or matifying agents such as titanium oxides.
35. Composition selon la revendication 34, caractérisée par le fait que chacun des additifs peut être présent à une concentration allant de 0 à 30% en poids du poids total de la composition.35. Composition according to claim 34, characterized in that each of the additives can be present at a concentration ranging from 0 to 30% by weight of the total weight of the composition.
36. Composition selon l'une quelconque des revendications 1 à 31, caractérisée par le fait qu'elle est aqueuse.36. Composition according to any one of claims 1 to 31, characterized in that it is aqueous.
37. Composition selon la revendication 36, caractérisée par le fait que le milieu aqueux contient un ou plusieurs solvants organiques.37. Composition according to claim 36, characterized in that the aqueous medium contains one or more organic solvents.
38. Composition selon la revendication 37, caractérisée par le fait que la concentration en solvant(s) varie de 0,5 à 20% et, de préférence, de 2 à 10% en poids par rapport au poids total de la composition.38. Composition according to claim 37, characterized in that the concentration of solvent (s) varies from 0.5 to 20% and, preferably, from 2 to 10% by weight relative to the total weight of the composition.
39. Composition selon l'une quelconque des revendications 36-38, caractérisée par le fait que le milieu aqueux contient du peroxyde d'hydrogène. 39. Composition according to any one of claims 36-38, characterized in that the aqueous medium contains hydrogen peroxide.
40. Composition selon l'une quelconque des revendications précédentes, caractérisée par le fait que la composition possède un pH allant de 4 à 12, de préférence de 7 à 11 ,5 et plus préférentiellement de 8 à 11.40. Composition according to any one of the preceding claims, characterized in that the composition has a pH ranging from 4 to 12, preferably from 7 to 11, 5 and more preferably from 8 to 11.
41. Composition selon la revendication 32, caractérisée par le fait que le polymère à squelette aminoplaste-éther se trouve dans une composition aqueuse.41. Composition according to claim 32, characterized in that the polymer with an aminoplast-ether skeleton is present in an aqueous composition.
42. Procédé de décoloration des fibres kératiniques, en particulier des fibres kératiniques humaines telles que les cheveux, consistant à appliquer sur les fibres, sèches ou humides, une composition prête à l'emploi contenant, dans un milieu approprié pour la décoloration, au moins un agent oxydant et au moins un polymère à squelette aminoplaste-éther défini dans l'une quelconque des revendications 1 à 12, et à la laisser agir pendant un temps de pause variant de 1 à 60 minutes, et de préférence de 10 à 45 minutes, à rincer les fibres, éventuellement à les laver au shampooing, puis à les rincer à nouveau, et à les sécher.42. Process for bleaching keratin fibers, in particular human keratin fibers such as the hair, consisting in applying to the fibers, dry or wet, a ready-to-use composition containing, in a medium suitable for bleaching, at least an oxidizing agent and at least one polymer with an aminoplast-ether skeleton defined in any one of claims 1 to 12, and allowing it to act for a pause time varying from 1 to 60 minutes, and preferably from 10 to 45 minutes , rinse the fibers, possibly wash them in shampoo, then rinse them again, and dry them.
43. Dispositif à deux compartiments ou « Kit » pour la décoloration des fibres kératiniques et en particulier des fibres kératiniques humaines telles que les cheveux, caractérisé par le fait que le premier compartiment contient au moins une poudre ou une composition aqueuse, et le deuxième compartiment une composition aqueuse, l'un au moins des deux compartiments contenant au moins un agent oxydant et l'un au moins des deux compartiments contenant au moins un polymère à squelette aminoplaste-éther. 43. Device with two compartments or “Kit” for bleaching keratin fibers and in particular human keratin fibers such as the hair, characterized in that the first compartment contains at least one powder or an aqueous composition, and the second compartment an aqueous composition, at least one of the two compartments containing at least one oxidizing agent and at least one of the two compartments containing at least one polymer with an aminoplast-ether skeleton.
EP00981415A 1999-12-08 2000-11-10 Bleaching composition for keratinic fibres, containing a thickening polymer with an ether plastic skeleton Expired - Lifetime EP1237531B1 (en)

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FR9915484A FR2802092B1 (en) 1999-12-08 1999-12-08 DECOLORING COMPOSITION FOR KERATINIC FIBERS COMPRISING A THICKENER POLYMER WITH AMINOPLASTE-ETHER SKELETON
FR9915484 1999-12-08
PCT/FR2000/003141 WO2001041725A1 (en) 1999-12-08 2000-11-10 Bleaching composition for keratinic fibres, containing a thickening polymer with an ether plastic skeleton

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Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TW572965B (en) * 2000-08-04 2004-01-21 Sued Chemie Ag Use of amphiphilic polymers or copolymers for the surface modification of reactive inorganic fillers
FR2815853B1 (en) * 2000-10-27 2002-12-27 Oreal HAIR COSMETIC COMPOSITION IN THE FORM OF FOAM COMPRISING AT LEAST ONE THICKENER POLYMER WITH AMINOPLASTE-ETHER SKELETON
DE20114179U1 (en) * 2001-08-28 2001-10-25 Wella Ag Colorants for keratin fibers
FR2842099B1 (en) * 2002-07-12 2004-09-10 Oreal ANHYDROUS PASTE FOR THE DECOLORATION OF HUMAN KERATINIC FIBERS
FR2864444B1 (en) * 2003-12-29 2006-02-03 Oreal ANHYDROUS DECOLORATION PASTE COMPRISING AT LEAST ONE CERAMIC TYPE COMPOUND AND METHOD IMPLEMENTING THE SAME
FR2904767A1 (en) * 2006-08-10 2008-02-15 Oreal Decoloring composition, useful for keratinous fibers e.g. human hair, comprises an oxidant and an amphoteric polymer e.g. acrylamide-dimethyldiallylammonium chloride-acrylic acid terpolymer
FR2904772B1 (en) * 2006-08-10 2010-11-12 Oreal COMPOSITION COMPRISING AN OXIDIZING AGENT AND ACRYLAMIDE / HALIDE POLYMER OF DIAKYLDIALLYLAMMONIUM / VINYL CARBOXYLIC ACID WITH HIGH ACRYLAMIDE RATES

Family Cites Families (62)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2271378A (en) 1939-08-30 1942-01-27 Du Pont Pest control
US2273780A (en) 1939-12-30 1942-02-17 Du Pont Wax acryalte ester blends
US2261002A (en) 1941-06-17 1941-10-28 Du Pont Organic nitrogen compounds
US2388614A (en) 1942-05-05 1945-11-06 Du Pont Disinfectant compositions
US2375853A (en) 1942-10-07 1945-05-15 Du Pont Diamine derivatives
US2454547A (en) 1946-10-15 1948-11-23 Rohm & Haas Polymeric quaternary ammonium salts
US2528378A (en) 1947-09-20 1950-10-31 John J Mccabe Jr Metal salts of substituted quaternary hydroxy cycloimidinic acid metal alcoholates and process for preparation of same
US2781354A (en) 1956-03-26 1957-02-12 John J Mccabe Jr Imidazoline derivatives and process
US2961347A (en) 1957-11-13 1960-11-22 Hercules Powder Co Ltd Process for preventing shrinkage and felting of wool
FR80759E (en) 1961-12-04 1963-06-14 Collection of milk by vacuum using trucks fitted with special equipment and bodywork adapted to this principle
US3227615A (en) 1962-05-29 1966-01-04 Hercules Powder Co Ltd Process and composition for the permanent waving of hair
US3206462A (en) 1962-10-31 1965-09-14 Dow Chemical Co Quaternary poly(oxyalkylene)alkylbis(diethylenetriamine) compounds
FR1400366A (en) 1963-05-15 1965-05-28 Oreal New compounds which can be used in particular for the treatment of hair
FR1492597A (en) 1965-09-14 1967-08-18 Union Carbide Corp New cellulose ethers containing quaternary nitrogen
CH491153A (en) 1967-09-28 1970-05-31 Sandoz Ag Process for the production of new cation-active, water-soluble polyamides
SE375780B (en) 1970-01-30 1975-04-28 Gaf Corp
FR2280361A2 (en) 1974-08-02 1976-02-27 Oreal HAIR TREATMENT AND CONDITIONING COMPOSITIONS
US4013787A (en) 1971-11-29 1977-03-22 Societe Anonyme Dite: L'oreal Piperazine based polymer and hair treating composition containing the same
LU64371A1 (en) 1971-11-29 1973-06-21
GB1394353A (en) 1972-06-29 1975-05-14 Gillette Co Hair treating composition
FR2368508A2 (en) 1977-03-02 1978-05-19 Oreal HAIR CONDITIONING COMPOSITION
US4277581A (en) 1973-11-30 1981-07-07 L'oreal Polyamino-polyamide crosslinked with crosslinking agent
US4172887A (en) 1973-11-30 1979-10-30 L'oreal Hair conditioning compositions containing crosslinked polyaminopolyamides
LU68901A1 (en) 1973-11-30 1975-08-20
US4025627A (en) 1973-12-18 1977-05-24 Millmaster Onyx Corporation Microbiocidal polymeric quaternary ammonium compounds
US3874870A (en) 1973-12-18 1975-04-01 Mill Master Onyx Corp Microbiocidal polymeric quarternary ammonium compounds
US3929990A (en) 1973-12-18 1975-12-30 Millmaster Onyx Corp Microbiocidal polymeric quaternary ammonium compounds
DK659674A (en) 1974-01-25 1975-09-29 Calgon Corp
US5196189A (en) 1974-05-16 1993-03-23 Societe Anonyme Dite: L'oreal Quaternized polymer for use as a cosmetic agent in cosmetic compositions for the hair and skin
BE829081A (en) 1974-05-16 1975-11-14 NEW COSMETIC AGENTS BASED ON QUATERNIZED POLYMERS
US4005193A (en) 1974-08-07 1977-01-25 Millmaster Onyx Corporation Microbiocidal polymeric quaternary ammonium compounds
US3966904A (en) 1974-10-03 1976-06-29 Millmaster Onyx Corporation Quaternary ammonium co-polymers for controlling the proliferation of bacteria
US4026945A (en) 1974-10-03 1977-05-31 Millmaster Onyx Corporation Anti-microbial quaternary ammonium co-polymers
US4025617A (en) 1974-10-03 1977-05-24 Millmaster Onyx Corporation Anti-microbial quaternary ammonium co-polymers
US4001432A (en) 1974-10-29 1977-01-04 Millmaster Onyx Corporation Method of inhibiting the growth of bacteria by the application thereto of capped polymers
US4027020A (en) 1974-10-29 1977-05-31 Millmaster Onyx Corporation Randomly terminated capped polymers
US4025653A (en) 1975-04-07 1977-05-24 Millmaster Onyx Corporation Microbiocidal polymeric quaternary ammonium compounds
US4027008A (en) 1975-05-14 1977-05-31 The Gillette Company Hair bleaching composition containing water-soluble amino and quaternary ammonium polymers
AT365448B (en) 1975-07-04 1982-01-11 Oreal COSMETIC PREPARATION
CH599389B5 (en) 1975-12-23 1978-05-31 Ciba Geigy Ag
US4031307A (en) 1976-05-03 1977-06-21 Celanese Corporation Cationic polygalactomannan compositions
LU76955A1 (en) 1977-03-15 1978-10-18
US4223009A (en) 1977-06-10 1980-09-16 Gaf Corporation Hair preparation containing vinyl pyrrolidone copolymer
US4157388A (en) 1977-06-23 1979-06-05 The Miranol Chemical Company, Inc. Hair and fabric conditioning compositions containing polymeric ionenes
LU78153A1 (en) 1977-09-20 1979-05-25 Oreal COSMETIC COMPOSITIONS BASED ON QUATERNARY POLYAMMONIUM POLYMERS AND PREPARATION PROCESS
US4131576A (en) 1977-12-15 1978-12-26 National Starch And Chemical Corporation Process for the preparation of graft copolymers of a water soluble monomer and polysaccharide employing a two-phase reaction system
FR2470596A1 (en) 1979-11-28 1981-06-12 Oreal COMPOSITION FOR THE TREATMENT OF KERATIN FIBERS BASED ON AMPHOTERIC POLYMERS AND CATIONIC POLYMERS
FR2471997B1 (en) 1979-12-21 1987-08-28 Oreal NOVEL POLYCATION POLYMERS, THEIR PREPARATION AND THEIR USE
FR2471777A1 (en) 1979-12-21 1981-06-26 Oreal NOVEL COSMETIC AGENTS BASED ON POLYCATIONIC POLYMERS, AND THEIR USE IN COSMETIC COMPOSITIONS
LU83349A1 (en) 1981-05-08 1983-03-24 Oreal AEROSOL FOAM COMPOSITION BASED ON CATIONIC POLYMER AND ANIONIC POLYMER
DE3273489D1 (en) 1981-11-30 1986-10-30 Ciba Geigy Ag Mixtures of quaternary polymeric acrylic ammonium salts, quaternary mono- or oligomeric ammonium salts and surfactants, their preparation and their use in cosmetic compositions
LU83876A1 (en) 1982-01-15 1983-09-02 Oreal COSMETIC COMPOSITION FOR TREATMENT OF KERATINIC FIBERS AND METHOD FOR TREATING THE SAME
US5139037A (en) 1982-01-15 1992-08-18 L'oreal Cosmetic composition for treating keratin fibres, and process for treating the latter
LU84708A1 (en) 1983-03-23 1984-11-14 Oreal THICKENED OR GELLIED HAIR CONDITIONING COMPOSITION CONTAINING AT LEAST ONE CATIONIC POLYMER, AT LEAST ONE ANIONIC POLYMER AND AT LEAST ONE XANTHANE GUM
DE3375135D1 (en) 1983-04-15 1988-02-11 Miranol Inc Polyquaternary ammonium compounds and cosmetic compositions containing them
US4719282A (en) 1986-04-22 1988-01-12 Miranol Inc. Polycationic block copolymer
LU86429A1 (en) 1986-05-16 1987-12-16 Oreal COSMETIC COMPOSITIONS CONTAINING A CATIONIC POLYMER AND AN ANIONIC POLYMER AS A THICKENING AGENT
MY105119A (en) 1988-04-12 1994-08-30 Kao Corp Low irritation detergent composition.
US5914373A (en) 1995-06-07 1999-06-22 United Catalysts, Inc. Water soluble aminoplast-ether copolymers
FR2769221B1 (en) * 1997-10-03 2000-01-14 Oreal OXIDIZING COMPOSITION AND USES FOR DYEING, PERMANENT DEFORMATION OR DECOLORATION OF KERATINIC FIBERS
FR2770522B1 (en) * 1997-11-04 2000-03-10 Oreal COMPOUNDS COMPRISING AN IMINOPHENOL FRAGMENT AND THEIR USE IN COSMETICS
US6187058B1 (en) * 1998-05-20 2001-02-13 Combe, Inc., Low water no volatile organic compound hair lightener and dyeing composition

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO0141725A1 *

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CA2393578A1 (en) 2001-06-14
DE60033685T2 (en) 2007-10-31
DE60033685D1 (en) 2007-04-12
AU779323B2 (en) 2005-01-20
FR2802092A1 (en) 2001-06-15
FR2802092B1 (en) 2002-01-18
US6800096B1 (en) 2004-10-05
ES2283332T3 (en) 2007-11-01
BR0016479A (en) 2002-09-10
WO2001041725A1 (en) 2001-06-14
EP1237531B1 (en) 2007-02-28
MXPA02005603A (en) 2002-09-18
JP2003516337A (en) 2003-05-13
AU1867001A (en) 2001-06-18
ATE355046T1 (en) 2006-03-15

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